Contact metathesis polymerization

ABSTRACT

A method for bonding a material to a first substrate surface that includes providing a catalyst at the first substrate surface and then contacting that surface with a material that undergoes a metathesis reaction to bond the material to the first substrate surface. There are two embodiments of this method—a coating process and an adhesive process. In the coating embodiment, the metathesizable material is contacted with the catalyst on the substrate surface so that it undergoes metathesis polymerization to form the coating. The adhesive process includes (a) providing a catalyst at the first substrate surface, (b) providing a metathesizable material between the first substrate surface and the second substrate surface, and (c) contacting the catalyst on the first substrate surface with the metathesizable material so that the metathesizable material undergoes a metathesis reaction and bonds the first substrate surface to the second substrate surface.

RELATION-BACK

[0001] This application is a continuation-in-part of copending SerialNo. 09/772,157, filed Jan. 29, 2001.

BACKGROUND OF THE INVENTION

[0002] The present invention relates to an improved method of bonding orcoating a material to a substrate surface and to bonded substrateshaving improved resistance to delamination at high temperatures.

[0003] U.S. Pat. No. 5,728,785 discloses crosslinked polycycloolefinspolymerized via a metathesis reaction in which a peroxide crosslinkingagent is mixed with the metathesizable monomer and catalyst anddecomposes at elevated temperatures to liberate reactive species whichreact with the resulting polymer to form crosslinks.

[0004] U.S. Pat. No. 5, 973,085 discloses a metathesizablebis-cycloolefins which have storage stability with one-componentmetathesis catalysts. The bis-cycloolefins undergo metathesispolymerization and self-crosslinking under thermal polymerization.

[0005] Co-pending Parent App. Ser. No. 09/209,202 discloses a contactmetathesis polymerization for coatings and adhesives that utilizes asurface metathesis reaction of a monomer, oligomer, polymer or mixturewhich contains a metathesis reactive functional group. Some of theexemplary monomers and mixtures of monomers illustrated for use in thatprocess include non-crosslinking and crosslinking monomers such asnorbornene, cycloalkenes, cycloalkadienes, cycloalkatrienes,cycloalkatetraenes, aromatic-containing cycloolefins and polycyclicnorbornenes and mixtures thereof. In the contact metathesispolymerization conducted upon the coating of a substrate surface or injoining two substrates, mixtures of certain crosslinking andnon-crosslinking monomers provide variable results.

[0006] It would be advantageous to provide contact metathesispolymerized coatings and adhesives with improved physical properties andbonding that can be applied without heat and are capable ofself-crosslinking without the necessity of a post-curing step.Furthermore it would be of industrial importance to provide contactmetathesis polymerized coatings and adhesives that exhibit highertemperature resistant bonds to the substrates joined or coated thereby.

SUMMARY OF THE INVENTION

[0007] According to the present invention there is provided a method forbonding a material to a first substrate surface that includes providinga catalyst at the first substrate surface and contacting the catalyst onthe surface with a mixture of at least one metathesizable monomer,oligomer or polymer and a metathesizable crosslinking comonomer whichundergoes a metathesis reaction to bond to the first substrate surface.There are two embodiments of this method—a coating process and anadhesive process.

[0008] In the coating embodiment, the metathesizable mixture of at leastone contact metathesis non-crosslinking monomer and crosslinking monomerthat is soluble in the non-crosslinking monomer is applied to thecatalyst on the substrate surface so that it undergoes metathesispolymerization on contact to form the coating or a component of thecoating. The resulting polymerized, crosslinked metathesized polymericmaterial itself becomes the coating or part of the coating. As usedherein, “coating” denotes any material that forms a film (continuous ordiscontinuous) on one side of a the substrate surface and serves afunctional purpose and/or aesthetic purpose. The substrate is notembedded in the coating and is distinguished from conventional reactiveinjection molding of a substrate embedded in the metathesized polymermatrix. Such functional purpose for a coating on one surface of asubstrate provides environmental protection of the coated surface fromexposure against corrosion, radiation, heat, solvents, and environmentalattack, mechanical properties such as lubricity, electric propertiessuch as conductive or resistive and catalytic properties. Paints areincluded in a “coating” according to this invention.

[0009] In the adhesive embodiment, the metathesis reaction is utilizedto provide a crosslinked metathesis polymer polymerized at the interfaceof two substrates to adhere the substrates together. The adhesiveembodiment is adaptable to adhere identical substrates or two distinctlydifferent substrate surfaces (crossbonding). In particular, there isprovided a method for bonding a first substrate surface to a secondsubstrate surface comprising (a) providing a catalyst at the firstsubstrate surface, (b) providing a metathesizable liquid mixturecomprising a crosslinking metathesizable monomer and non-crosslinkingmetathesizable monomer wherein the crosslinking metathesizable monomeris dissolved in the non-crosslinking liquid monomer, the mixturepolymerized between the first substrate surface and the second substratesurface or providing a metathesizable mixture as a component of thesecond substrate, and (c) contacting the catalyst on the first substratesurface with the metathesizable mixture to effect the metathesisreaction and bond the first substrate surface to the second substratesurface with a crosslinked metathesized polymer adhesive.

[0010] According to a first adhesive embodiment as shown in FIG. 1, themetathesizable mixture material is present as part of a compositioninterposed between the catalyst on the first substrate surface and thesecond substrate surface. In other words, the metathesizable material issimilar to a conventional adhesive in that it is a composition that isdistinct from the two substrates when applied. According to a secondadhesive embodiment as shown in FIG. 2, the second substrate is madefrom or includes the metathesizable material and contacting this secondsubstrate with the catalyst on the first substrate surface creates anadhesive interlayer between the first and second substrates. Theadhesive interlayer comprises a thin layer of the metathesizable secondsubstrate that has undergone metathesis.

[0011] There is also provided a manufactured article that includes afirst substrate surface, a second substrate surface and an adhesivelayer interposed between and bonding the first and second substratesurfaces, wherein the first substrate surface comprises an elastomericmaterial and the adhesive layer comprises a metathesis polymer.

[0012] The invention offers the unique ability to form a strong adhesivebond on a variety of substrate surfaces (including difficult-to-bondpost-vulcanized elastomeric materials and thermoplastic elastomers) atnormal ambient conditions with a minimal number of steps and surfacepreparation. The method also avoids the use of volatile organic solventssince it is substantially 100 percent reactive and/or can be done withaqueous carrier fluids.

[0013] The adhesive method of the invention is especially useful to bonda fibrous substrate. The present invention provides for a method forbonding a fibrous substrate surface to a second substrate surfacecomprising (a) providing a catalyst at the fibrous substrate surface;(b) contacting the catalyst on the fibrous substrate surface with ametathesizable material so that the metathesizable material undergoes ametathesis reaction; and (c) contacting the fibrous substrate surfacewith a second substrate surface. Alternatively, the fibrous substratecan be coated according to the coating embodiment.

[0014] The adhesive method of the invention is especially useful to makea tire laminate wherein the catalyst is applied to a tire tread or tirecarcass, the metathesizable material is applied to the tire tread ortire carcass to which the catalyst has not been applied, and thecatalyst-applied tire tread or tire carcass and the metathesizablematerial-applied tire tread or tire carcass are bonded together. Thismethod allows for tire retreading with no or minimal heat and pressure,does not require significant curing time and should reduce the cost ofequipment installation.

[0015] According to a further embodiment of the invention, the methodcan be used to make multilayer structures for either coating or adhesiveapplications. In this embodiment, the catalyst and the metathesizablematerial are initially applied to the first substrate surface asdescribed above. The catalyst site, however, propagates within thecoating layer where it remains as a stable active site for a subsequentreaction with a metathesizable material. In other words, active catalystremains on the new surface that has been created from the metathesizablematerial. A second metathesizable material then is contacted with this“living” surface and another new layer is created. This process can berepeated until the concentration of active catalyst remaining on thesurface has diminished to a level that is no longer practically useful.It should be noted that the catalysts typically are not consumed ordeactivated and thus there may be no need for excess catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016]FIG. 1 depicts a preferred embodiment of a first embodiment of aprocess for bonding two substrates according to the invention;

[0017]FIG. 2 depicts a second embodiment of a process for bonding twosubstrates according to the invention;

[0018]FIG. 3 depicts a bonding process according to the inventionwherein the catalyst is included in a polymer matrix; and

[0019]FIG. 4 depicts a “living” coating process according to theinvention.

[0020]FIG. 5 depicts the “toughness” of an adhesive bond preparedaccording to the invention at variable peel temperatures.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Unless otherwise indicated, description of components in chemicalnomenclature refers to the components at the time of addition to anycombination specified in the description, but does not necessarilypreclude chemical interactions among the components of a mixture oncemixed.

[0022] As used herein, the following terms have certain meanings:

[0023] “ADMET” means acyclic diene olefin metathesis;

[0024] “catalyst” also includes initiators, co-catalysts and promoters;

[0025] “coating” includes a coating that is intended to be the final orouter coating on a substrate surface and a coating that is intended tobe a primer for a subsequent coating;

[0026] “fibrous substrate” means a woven or non-woven fabric, amonofilament, a multifilament yarn or a fiber cord;

[0027] “filmogenic” means the ability of a material to form asubstantially continuous film on a surface;

[0028] “metathesizable material” means a single or multi-componentcomposition that includes at least one component that is capable ofundergoing a metathesis reaction at ambient mild elevated temperatures(up to about 60° C.);

[0029] “non-fibrous substrate” means any substrate type other than afiber (non-fibrous substrate includes a composite substrate thatincludes fibers as one component such as fiber-reinforced plastics);

[0030] “normal ambient conditions” means temperatures typically found inminimal atmosphere control workplaces (for example, about −20° C. toabout 40° C.), pressure of approximately 1 atmosphere and an airatmosphere that contains a certain amount of moisture;

[0031] “ROMP” means ring-opening metathesis polymerization;

[0032] “room temperature” means about 10° C. to about 40° C., typicallyabout 20° C. to about 25° C.;

[0033] “substantially cured elastomer” and “post-vulcanized elastomer”are used interchangeably and means thermoset polymers above T_(g) forthat polymer and thermoplastic polyolefins (substantially cured orpost-vulcanized elastomers typically are not capable of flow); and

[0034] “surface” means a region of a substrate represented by theoutermost portion of the substrate defined by material/air interface andextending into the substrate from about 1 atomic layer to many thousandsof atomic layers.

[0035] The polymerization bonding adhesion or polymerization coatingthat takes place according to the present invention occurs via ametathesis reaction. The adhesives and coatings are relatively thin, andcover substrates that are thicker than the bond-line or coatingthickness. Uniform coatings are formed on surfaces of a relativelyinfinite surface area in relation to the thickness of the adhesivebondline or coating.

[0036] Various metathesis reactions are described in Ivin, K. J. andMol, J. C., Olefin Metathesis and Metathesis Polymerization (AcademicPress 1997). The metathesis reaction could be a cross-metathesisreaction, an ADMET, a ring-closing metathesis reaction or, preferably, aROMP. It should be recognized that the surface metathesis polymerizationthat occurs in this invention is very different than bulk (includingreaction injection molding), emulsion or solution metathesispolymerization in which a metathesizable monomer and a catalyst aremixed together into a single composition to effect the metathesisreaction. Bulk metathesis polymerization, particularly reactioninjection molding, of norbornene monomer for producing molded articlesmade of the resulting polynorbornene is known. For example, U.S. Pat.No. 4,902,560 teaches a method for making a glass fiber-reinforcedpolydicyclopentadiene article that involves saturating an uncoated wovenglass fabric with a polymerizable liquid that includes dicyclopentadienemonomer and catalyst, subjecting the saturated fabric to reactioninjection molding and post-curing the resultant structure. According tothe present invention, the resulting metathesis polymer forms afilmogenic adhesive or coating rather than a molded article.

[0037] The metathesizable material used in the invention is any materialthat is capable of undergoing a metathesis polymerization andcrosslinking via metathesis when contacted with a metathesis catalyst.The metathesizable material containing metathesizable crosslinkingfunction may be a monomer, oligomer, polymer or mixtures thereof with acrosslinking metathesizable monomer. Preferred metathesizable materialsare those that include at least one metathesis reactive functional groupsuch as olefinic materials. The metathesizable material or component canhave a metathesis reactive moiety functionality ranging from 1 to about1000, preferably from about 1 to about 100, more preferably from about 1to 10, mol metathesizable moiety/mol molecule of metathesizablecomponent. In addition, materials capable of undergoing ROMP typicallyhave “inherent ring strain” as described in Ivin et al. at page 224,with relief of this ring strain being a driving force for thepolymerization. Materials capable of undergoing ADMET typically haveterminal or near-terminal unsaturation. The principal material consistsof monomer, oligomer or polymer that by itself does not undergocrosslinking at a significant level (low level). The low level ofcrosslinking is comparable to the level of crosslinking thatnorbornadiene or dicyclopentadiene undergoes itself in a metathesisreaction. It is the additional crosslink density provided by a minorproportion (0.5-20 mol %) of a metathesizable crosslinking comonomerthat provides the improved bonding and coating properties at hightemperatures.

[0038] Illustrative metathesizable materials are those that include anunsaturated functional group such as ethene, α-alkenes, acyclic alkenes(i.e., alkenes with unsaturation at β-position or higher), acyclicdienes, acetylenes, cyclic alkenes and cyclic polyenes. Cyclic alkenesand cyclic polyenes, especially cycloolefins, are preferred. When cyclicalkenes or polyenes are the metathesizable material, the metathesisreaction is a ROMP.

[0039] A monomer or oligomer is particularly useful when themetathesizable material itself is intended to form a coating on thesubstrate surface or when the metathesizable material itself is intendedto act as an adhesive for bonding one substrate surface to anothersubstrate surface. Monomers are especially useful because they candiffuse into the substrate surface when they are applied. Particularlyuseful as monomers by themselves, as monomers for making oligomers, orfor functionalizing other types of polymers, are cycloolefins such asnorbornene, cycloalkenes, cycloalkadienes, cycloalkatrienes,cycloalkatetraenes, aromatic-containing cycloolefins and mixturesthereof. Illustrative cycloalkenes include cyclooctene,hexacycloheptadecene, cyclopropene, cyclobutene, cyclopentene,cyclohexene, cycloheptene, cyclononene, cyclodecene, cyclododecene,paracyclophene, and ferrocenophene. Illustrative cycloalkadienes includecyclooctadiene and cyclohexadiene. Illustrative cycloalkatrienes includecyclooctatriene. Illustrative cycloalkatetraenes includecyclooctatetraene.

[0040] Norbornene monomers are especially suitable. As used herein,“norbornene” means any compound that includes a norbornene ring moiety,including norbornene per se, norbornadiene, substituted norbornenes, andpolycyclic norbornenes. As used herein, “substituted norbornene” means amolecule with a norbornene ring moiety and at least one substituentgroup. As used herein, “polycyclic norbornene” mean a molecule with anorbornene ring moiety and at least one additional fused ring.Illustrative norbornenes include those having structures represented bythe following formulae:

[0041] wherein X is CH₂, CHR³, C(R³)₂, O, S, N—R³, P—R³, O═P—R³,Si(R³)₂, B—R³ or As—R³; each R¹ is independently H, CH₂, alkyl, alkenyl(such as vinyl or allyl), cycloalkyl, cycloalkenyl, aryl, alkaryl,aralkyl, halogen, halogenated alkyl, halogenated alkenyl, alkoxy,oxyalkyl, carboxyl, carbonyl, amido, (meth)acrylate-containing group,anhydride-containing group, thioalkoxy, sulfoxide, nitro, hydroxy, keto,carbarnato, sulfonyl, sulfinyl, carboxylate, silanyl, cyano or imido; R²is a fused aromatic, aliphatic or hetero cyclic or polycyclic ring; andR³ is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkylor alkoxy. The carbon-containing R groups may have up to about 20 carbonatoms.

[0042] Exemplary substituted norbornene monomers includemethylidenenorbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene,5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene,5-octyl-2-norbornene, ethylidenenorbornene (ENB),5-dodecyl-2-norbornene, 5-isobutyl-2-norbornene,5-octadecyl-2-norbornene, 5-isopropyl-2-norbornene,5-phenyl-2-norbornene, 5-p-toluyl-2-norbornene,5-α-naphthyl-2-norbornene, 5-cyclohexyl-2-norbornene,5-isopropenyl-norbornene, 5-vinyl-norbornene, 5,5-dimethyl-2-norbornene,5-norbornene-2-carbonitrile, 5-triethoxysilyl-2-norbornene,5-norborn-2-yl acetate, 7-oxanorbornene, 5-norbornene-2,3-carboxylicacid, 5-norbornene-2,2-dimethanol, 2-benzoyl-5-norbornene,5-norbornene-2-methanol acrylate, 2,3-di(chloromethyl)-5-norbornene,2,3-hydroxymethyl-5-norbornene di-acetate and their stereoisomers andmixtures thereof.

[0043] Exemplary polycyclic norbornene monomers include tricyclicmonomers such as dicyclopentadiene (DCPD):

[0044] and dihydrodicyclopentadiene:

[0045] tetracyclic monomers such as tetracyclododecene:

[0046] , pentacyclic monomers such as tricyclopentadiene:

[0047] , hexacyclic monomers such as hexacycloheptadecene:

[0048] , heptacyclic monomers such as tetracyclopentadiene;

[0049] nonacyclic monomers such as pentacyclopentadiene:

[0050] and the corresponding substituted polycyclic norbornenes.

[0051] Structures of exemplary cycloolefins are shown below

[0052] wherein R in (32) are independently selected from H, CH₂, alkyl,alkenyl (such as vinyl or allyl), cycloalkyl, cycloalkenyl, aryl,alkaryl, aralkyl, halogen, halogenated alkyl, halogenated alkenyl,alkoxy, oxyalkyl, carboxyl, carbonyl, amido, anhydride-containing group,thioalkoxy, sulfoxide, nitro, hydroxy, keto, carbarnato, sulfonyl,sulfinyl, carboxylate, silanyl, cyano or imido; fused aromatic,aliphatic or heterocyclic or polycyclic ring, and

[0053] wherein X in (51) is CH₂, CHR³, C(R³)₂, O, S, N—R³, P—R³,O═P—R³,Si(R³)₂, B—R³ or As-R³; and R and R′ in (51) is independently H, CH₂,alkyl, alkenyl (such as vinyl or allyl), cycloalkyl, cycloalkenyl, aryl,alkaryl, aralkyl, halogen, halogenated alkyl, halogenated alkenyl,alkoxy, oxyalkyl, carboxyl, carbonyl, amido, (meth)acrylate-containinggroup, anhydride-containing group, thioalkoxy, sulfoxide, nitro,hydroxy, keto, carbarnato, sulfonyl, sulfinyl, carboxylate, silanyl,cyano or imido; fused aromatic, aliphatic or heterocyclic or polycyclicring. Carbon-containing R and R′ groups may have up to about 20 carbonatoms, and polycyclic esters derived from the Diels-Alder reaction of anunsaturated carboxylic such as acrylic or methacrylic acid andcycloolefin, e.g. dicyclopentadiene, followed by esterification using apolyol, e.g., diol, triol, tetraol, etc. Examples of the polycyclicesters based on acrylic acid and diol or triol, are

[0054] A crosslinker can be made by Diels-Alder reaction of acycloolefin such as cyclopentadiene and an unsaturated carboxylic acidfollowed by reaction with a diisocyanate and expulsion of CO₂ to give anamide, or by reduction of the acid to the alcohol followed by reactionwith a diisocyanate to give a carbarnate.

[0055] A number of other polycyclic metathesizable monomers within thescope of the above structures are known, such as bis-norbornenes, and asother examples 13-19, 35 and 44- and 51 are metathesizable crosslinkingmonomers. Crosslinking metathesizable comonomers are characterized bythe presence of two or more metathesizable double bonds capable ofpolymerizing by a metathesis reaction at ambient conditions. In amixture of a monomer that contains one metathesizable group, i.e., anon-crosslinking monomer, oligomer or polymer, with a monomer thatcontains at least two metathesizable groups, it has been found that oncontact metathesis, the polymerization of the mixture at the surface ofthe substrate results in a crosslinked polymer having improved physicalproperties provided that the crosslinking monomer is soluble at themetathesis polymerizing temperature at a level of least at 0.5 mole % inthe other principal monomer(s), and provided the metathesizablecrosslinking monomer has a reactivity ratio similar to the othermonomer(s) in the metathesis polymerization. Some metathesizablecrosslinking comonomers require heating the monomer mixture to 40° C. upto the boiling point of the mixture in order to dissolve sufficientamounts of crosslinking monomer. The solubility, and determination oftemperature at which sufficient solubility of the crosslinkingmetathesizable comonomer will occur is readily determinable by combiningthe monomers and observing whether dissolution takes place or thetemperature at which dissolution takes place.

[0056] Crosslinked polymers resulting from contact metathesispolymerization of a mixture of materials, one being a minor moleproportion of a metathesizable crosslinking monomer, will contain from80-99.5 mol % of a principal metathesized material and from 0.5-20 mol %of copolymerized metathesizable crosslinking monomer that is based on atleast two metathesizable unsaturated moieties. The mol % of crosslinkingmetathezible monomer incorporated in the resulting crosslinked polymeris critical to providing improved adhesive and coating performance. Thelower critical limit is 0.5 mole % of metathesizable crosslinkingmonomer incorporated into the crosslinked polymer. The lower limit canbe limited to the degree of solubility of the crosslinking monomer inthe mixture of metathesizable monomers/materials. A minimum solubilityof metathesizable monomer in admixture with the principal monomeraccording to the invention is therefore 0.5 mol %. Many metathesizablecrosslinking comonomers are readily soluble at room temperature in arange of from 0.5 to 20 mol %. Some methesizable crosslinikingcomonomers will dissolve in the monomer/material mixture with heating.The solubility can be readily determined empirically by quantitativelyobserving the dissolution of metathesizable crosslinking monomer in theprincipal metathesizable material by visual inspection of the mixture ina test tube. Compounds 13-19, 35 and 44-51 are soluble in a monomermixture in a range of 0.5%-20 mol % at room temperature or under mildheating.

[0057] The type of principal or primary metathesizable material can haveany molecular weight ranging from monomeric to oligomeric to polymericthat contains functionality capable of undergoing ROMP. Other examplesof principal metathesizable monomers useful for this invention are shownbelow and referenced.

[0058] For example, the norbornene containing poly(ester-amide)s is asuitable crosslinker, and (Ikeda, A.; Tsubata, A.; Kameyama, A.;Nishikubo, T. “Synthesis and Photochemical Properties ofPoly(ester-amide)s Containing Norbomadiene (NBD) Residues,” J. Poly.Sci.: Part A: Polymer Chemistry, 1999, 37, 917) is useful as a ROMP andCMP crosslinker.

[0059] See, Coleman, C. G.; McCarthy, T. J. “Tricyclooctadiene: ACrosslinking Agent for Olefin Metathesis Polymerization,” PolymerPreprints, 1988, 28, 283. This material is available by dimerization ofcis-3,4-dichlorocyclobutene (Paquette, L. A.; Carmody, M. J. J. Amer.Chem. Soc., 1976, 98, 8175.).

[0060] See, Bazan, G. C.; Schrock, R. R. “Synthesis of Star BlockCopolymers by Controlled Ring-Opening Metathesis Polymerization,”Macromolecules, 1991, 24, 817. Saunders, R. S.; Cohen, R. E.; Wong, S.J.; Schrock, R. R. “Synthesis of Amphiphilic Star Block Copolymers UsingRing-Opening Metathesis Polymerization,” Macromolecules, 1992, 25, 2055.

[0061] (see 17 above)

[0062] See, Stille, J. K.; Witherell, D. R. “Influence of HydrogenCrowding on the Rates of Reactions. The Addition of cis Reagents to theDimethanonaphthalene Ring System,” J. Amer. Chem. Soc., 1964, 86, 2188.

[0063] See, Stille, J. K.; Frey, D. A. “Tetracyclic Dienes. I. TheDiels-Alder Adduct of Norbornadiene and Cyclopentadiene,” J. Amer. Chem.Soc., 1959, 81, 4273. (See 18 above)

[0064] An optional heat-reactive peroxide compound can be included inthe metathesizable material that enables crosslinking of the bondedadhesive or coating by converting residual unsaturation in a post-cureheating step. The crosslinking agent generally comprises a peroxide thatdecomposes into reactive species forming crosslinks during post-cure.

[0065] Examples of suitable peroxides include known compounds such asalkyl peroxides, particularly tert-butyl peroxide or di-t-butylperoxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane, benzoyl peroxide andother diacyl peroxides, hydroperoxides such as cumene hydroperoxide,peresters such as t-butylperoxybenzoate; ketone hydroperoxides such asmethyl ethyl ketone hydroperoxide. Commercially availableorganoperoxides which are suitable are available from Elf Atochem N.V.under the LUPERSOL® mark, for example LUPERSOL 130, believed to containa mixture of 2,5-dimethyl-2,5-di(tert-butylperoxy) hexyne-3 anddi-t-butyl peroxide, and LUPERSOL 101, containing2,5-dimethyl-2,5-di(tert-butylperoxy) hexane and di-tert-butyl peroxide.See Examples 36 E and H.

[0066] The optional peroxide catalyst is mixed with the metathesizablematerial prior to contacting with the metathesis catalyst. Typicalpost-baking temperatures are those above the decomposition temperatureof the catalyst, and range from approx. 60° C. -120° C. and for dwelltimes of from one to three half lives of the selected peroxide at thepost-bake temperature. The post-bake curing conditions can readily bepredetermined according to the known or recommended curing conditionsfor the selected peroxide catalyst.

[0067] The preferred metathesis catalysts applied to the substratesurface and contacted with a mixture of metathesizable material,metathesizable crosslinker and optional peroxide crosslinker areruthenium, osmium or iridium carbene complexes having a structurerepresented by

[0068] wherein M is Os, Ru or Ir; each R¹ is the same or different andis H, C₂₋₂₀ alkenyl, C₂₋₂₀ alkynyl, C₁₋₂₀ alkyl, aryl, alkaryl, aralkyl,C₁₋₂₀ carboxylate, C₁₋₂₀ alkoxy, C₂₋₂₀ alkenyloxy, alkenylaryl, C₂₋₂₀alkynylalkoxy, aryloxy, C₂₋₂₀ alkoxycarbonyl, alkylthio, alkylsulfonylor alkylsulfinyl; X is the same or different and is an anionic ligandgroup; and L is the same or different and is a neutral electron donorgroup. The metathesizable material polymerizes via the contactmetathesis mechanism and then the peroxide crosslinking agentdecomposes, e.g., at an elevated temperature to form active specieswhich reacts with ethylenic groups to form crosslinks in the polymer.Preferably a crosslinked metathesized polymer results from contactmetathesis polymerization in the absence of a post-cure application ofheat. That is, during contact metathesis, the conversion ofmetathesizable material mixture containing a crosslinking monomer occurson contact with the catalyst at the surface of a substrate and issubstantially completed, resulting in a crosslinked polymer underambient conditions. The crosslinked polymer formed during contactmetathesis polymerization exhibits improved tensile strength andadhesion at elevated temperatures above its Tg, while the lowertemperature (room temp and below) tensile and adhesion properties aresurprisingly not diminished.

[0069] The metathesizable moieties of crosslinking monomers shown above,can be selected, such as in structures 13-19, 35, 50 and 51 to exhibit areactivity that is similar to selected principal metathesizablematerials, and on contact with the catalyst at the surface of asubstrate, crosslinking occurs in the propagating polymer at ambient ormildly elevated conditions, depending upon the limit of solubility ofthe metathesizable crosslinking monomer in the metathesizable mixture.

[0070] A preferred principal metathesizable monomer isethylidenenorbornene, particularly 5-ethylidene-2-norbornene (referredto herein as “ENB”), and dicyclopentadiene (referred to herein as“DCPD”). Ethylidenenorbornene surprisingly provides superior performanceover a wide variety of substrates.

[0071] When used as a coating or an adhesive the metathesizable monomeror oligomer mixture may be used by itself in a substantially pure formor technical grade. Of course, as described below the metathesizablemonomer or oligomer can be included in a mixture with other componentsor it can be substantially diluted with a solvent or carrier fluid. Asused herein, “technical grade” means a solution that includes at leastabout 90 weight % monomer or oligomer. The advantage of using atechnical grade is that the metathesizable composition is approximately100% reactive and thus there are no workplace or environmental problemscaused by volatile organic compounds or performance problems caused bynon-reactive additives and there is no need for purification.

[0072] Alternatively, the metathesizable monomer or oligomer mixture canbe included in a multi-component composition such as an emulsion,dispersion, solution or mixture. In other words, the metathesizablematerial mixture can be a multi-component composition that includes atleast one metathesizable component such as a metathesizable monomer oroligomer. Preferably, such metathesizable component-containingcomposition is in the form of a liquid, paste or meltable solid when itis applied. The metathesizable liquid composition can be prepared bymixing together the components according to conventional means and thencan be stored for an extended time period prior to use (referred toherein as “shelf life”).

[0073] For example, the metathesizable monomer mixture can be dissolvedor dispersed in conventional organic solvents such as cyclohexane,methylene chloride, chloroform, toluene, tetrahydrofuran,N-methylpyrrolidone, methanol, ethanol or acetone or in water. Oneparticularly useful composition could include the metathesizablemonomer/oligomer mixture dissolved in a polymer such as a polyester,polyurethane, polycarbonate, epoxy or acrylic. The metathesizablemixture can also be included in a multi-component composition whereinthe metathesis polymerization occurs in the presence of a pre-formedand/or simultaneously forming material resulting in the formation of aninterpenetrating polymer network (IPN).

[0074] The metathesizable composition (either monomer mixture alone ormulti-component) preferably is substantially about 100% reactive with noinert volatile organic components to remove upon formation of coating oradhesive polymer. In other words, the composition does not includesubstantially any liquid amount that does not react to form a solid.

[0075] According to another embodiment shown in FIG. 2, the secondsubstrate for bonding to the first substrate includes a metathesizablecomponent. The metathesizable material can be present as a chemically-or ionically-bonded portion of the substrate material or it can bepresent simply in the form of a physical mixture (e.g., hydrogenbonding).

[0076] Any metathesis catalyst that is capable of polymerizing themetathesizable material upon contact can be used. The well-definedmetathesis catalysts disclosed herein typically have air- andwater-stability enabling ease of application to a wide variety ofsubstrates, and have adequate shelf-stability after applied to thesubstrate surface over days, and up to several months or more. Inparticular, for normal ambient conditions bonding, the metathesiscatalyst should be capable of maintaining its activity in the presenceof oxygen and moisture for a reasonable period of time after applicationto the substrate material and until the metathesizable material isbrought into contact with the catalyst. Experimental tests haveindicated that the ruthenium catalysts can remain active for at least 30days after coating on the substrate surface.

[0077] There are numerous known metathesis catalysts that might beuseful in the invention. Transition metal carbene catalysts are wellknown. Illustrative metathesis catalyst systems include rheniumcompounds (such as Re₂O₇/Al₂O₃, ReCl₅/Al₂O₃, Re₂O7/Sn(CH₃)₄, andCH₃ReO₃/Al₂O₃-SiO₂); ruthenium compounds (such as RuCl₃, RuCl₃(hydrate),K₂[RuCl₅-H₂O ], [Ru(H₂O )₆](tos)₃ (“tos” signifies tosylate),ruthenium/olefin systems (meaning a solution or dispersion of preformedcomplex between Ru and olefin (monomer) that also includes a β-oxygen inthe presence or absence of a soluble or dispersed polymer where thepolymer can be an oligomer or higher molecular weight polymer preparedby metathesis or other conventional polymerization synthesis), andruthenium carbene complexes as described in detail below); osmiumcompounds (such as OsCl₃, OsCl₃(hydrate) and osmium carbene complexes asdescribed in detail below); molybdenum compounds (such as molybdenumcarbene complexes (such as t-butoxy and hexafluoro-t-butoxy systems),molybdenum pentachloride, molybdenum oxytrichloride, tridodecylammoniummolybdate, methyltricaprylammonium molybdate, tri(tridecyl)ammoniummolybdate, and trioctylammonium molybdate); tungsten compounds (such astungsten carbene complexes such as t-butoxy and hexafluoro-t-butoxysystems, WCl₆ (typically with a co-catalyst such as SnR₄ or PbR₄,tungsten oxytetrachloride, tungsten oxide tridodecylammonium tungstate,methyltricaprylammonium tungstate, tri(tridecyl)ammonium tungstate,trioctylammonium tungstate, WCl₆/CH₃CH₂OH/CH₃CH₂AlCl₂, WO₃/SiO₂/Al₂O₃,WCl₆/2,6-C₆H₅-C₆H₅OH/SnR₄, WCl₆/2,6—Br—C₆H₃OH/SnR₄,WOCl₄/2,6-C₆H₅-C₆H₅OH/SnR₄, WOCl₄/2,6-Br—C₆H₃OH/SnR₄); TiCl₄/aluminumalkyl; NbO_(x)/SiO₂/iso-butyl AlCl₂; and MgCl₂. R₄ referred to in thiscontext means an alkyl group. As indicated above, some of thesecatalysts, particularly tungsten, require the presence of additionalactivator or initiator systems such as aluminum, zinc, lead or tinalkyl. Preferred catalysts are ruthenium compounds, molybdenum compoundsand osmium compounds.

[0078] Particularly preferred are ruthenium, osmium or iridium carbenecomplexes having a structure represented by

[0079] wherein M is Os, Ru or Ir; each R¹ is the same or different andis H, alkenyl, alkynyl, alkyl, aryl, alkaryl, aralkyl, carboxylate,alkoxy, allenylidenyl, indenyl, alkylalkenylcarboxy, alkenylalkoxy,alkenylaryl, alkynylalkoxy, aryloxy, alkoxycarbonyl, alkylthio,alkylsulfonyl, alkylsulfinyl, amino or amido; X is the same or differentand is either an anionic or a neutral ligand group; and L is the same ordifferent and is a neutral electron donor group. The carbon-containingsubstituents may have up to about 20 carbon atoms. Preferably, X is Cl,Br, I, F, CN, SCN, or N₃, O-alkyl or O-aryl. Preferably, L is aheterocyclic ring or Q(R²)_(a) wherein Q is P, As, Sb or N; R² is H,cycloalkyl, alkyl, aryl, alkoxy, arylate, amino, alkylamino, arylamino,amido or a heterocyclic ring; and a is 1, 2 or 3. Preferably, M is Ru;R¹ is H, phenyl (“Ph”), —CH═C(Ph)₂, —CH═C(CH₃)₂ or —C(CH₃)₂Ph; L is atrialkylphosphine such as PCy₃ (Cy is cyclohexyl or cyclopentyl),P(isopropyl)₃ or PPh₃; and X is Cl. Particularly preferred catalystsinclude tricyclohexyl phosphine ruthenium carbenes, especiallybis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride(designated herein by RuCl₂(PCy₃)₂=CHPh). Such ruthenium and osmiumcarbene catalysts are described, for example, in U.S. Pat. Nos.5,312,940 and 5,342,909, both incorporated herein by reference; Schwab,P.; Grubbs, R. H.; Ziller, J. W., Journal of the American ChemicalSociety, 1996, 118, 100; Schwab, P.; France, M. B., Ziller, J. W.;Grubbs, R. H., Angew. Chem. Int. Ed., 1995, 34, 2039; and Nguyen, S. T.;Grubbs, R. H., Journal of the American Chemical Society, 1993, 115,9858.

[0080] Additionally preferred catalysts within this group are thosecatalysts wherein the L groups are trialkylphosphines,imidazol-2-ylidene or dihydroimidazol-2-ylidene based systems, eithermixed or the same. Examples of these catalysts includeN,N′-disubstituted 4,5-dihydroimidazol-2-ylidene substituted rutheniumcarbene, a N,N′-disubstituted imidazol-2-ylidene substituted rutheniumcarbene, a mixed phosphine-dihydroimidazol-2-ylidene substitutedruthenium carbene or a mixed phosphine-imidazol-2-ylidene substitutedruthenium carbene. Particularly preferred among these aretricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium(IV) dichloride, ortricyclohexylphosphine[1,3-bis(2,3,6-trimethylphenyl)-4,5-imidazol-2-ylidene][benzylidene]ruthenium (IV) dichloride. The following are some usefulcatalysts (Cy=cyclohexyl, R₂=alkyl and aryl groups):

[0081] Useful catalysts are described in articles such as Ahmed, M.;Garrett, A. G. M.; Braddock, D. C.; Cramp, S. M.; Procopoiou, P. A.Tetrahedron Letters 1999, 40, 8657; Olivan, M.; Caulton, K. G. J. Chem.Soc., Chem. Commun. 1997, 1733; Amoroso, D.; Fogg, D. E. Macromolecules2000, 33, 2815; Fürstner, A.; Hill, A. F.; Liebl, M.; Wilton-Ely, J. D.E. T. J. Chem. Soc., Chem. Commun., 1999, 601; Robson, D. A.; Gibson, V.C.; Davies, R. G.; North, M. Macromolecules 1999, 32, 6371; Schwab, P.;France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem. Int. Ed. 1995,34, 2039; Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc.1996,118, 100; Ulman, M.; Belderrain, T. R.; Grubbs, R. H. TetrahedronLett. 2000, 4689; M. Scholl; S. Ding; C. W. Lee; Grubbs, R. H. OrganicLett. 1999, 1, 953; Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R.H. Tetrahedron Lett. 1999,40, 2247; Belderrain, T. R.; Grubbs, R. H.Organometallics 1997, 16, 4001; Ulman, M.; Belderrain, T. R.; Grubbs, R.H. Tetrahedron Lett. 2000, 4689; Sanford, M. S.; Henling, L. M.; Day, M.W.; Grubbs, R. H. Angew. Chem. Int. Ed. 2000, 39, 3451; Lynn, D. M.;Mohr, B.; Grubbs, R. H.; Henling, L. M.; Day, M. W. J. Am. Chem. Soc.2000, 122, 6601; Mohr, B.; Lynn, D. M.; Grubbs, R. H. Organometallics1996,15, 4317; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem.Soc. 1993,115, 9858; Weskamp, T.; Schattenmann, W. C.; Spiegler, M.;Herrmann, W. A. Angew. Chem. Int. Ed. 1998, 37, 2490; Hansen, S. M.;Volland, M. A. O.; Rominger, F.; Eisentrager, F.; Hofmann, P. Angew.Chem. Int. Ed. 1999, 38, 1273; J. S. Kingsbury, J. S.; Harrity, J. P.A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999,121, 791;Wolf, J.; Stuer, W.; Grunwald, C.; Werner, H.; Schwab, P.; Schulz, M.Angew. Chem. Int. Ed. 1998, 37, 1124.

[0082] Another ruthenium carbene complex that may be useful is abimetallic catalyst having a structure represented by

[0083] wherein M is Ru, Os or Rh. Such a catalyst is disclosed in Dias,E. L.; Grubbs, R. H., Organometallics, 1998, 17, 2758.

[0084] Preferred molybdenum or tungsten catalysts are those representedby the formula:

[0085] wherein M is Mo or W; X is O or S; R¹ is an alkyl, aryl, aralkyl,alkaryl, haloalkyl, haloaryl, haloaralkyl, or a silicon-containinganalog thereof; R² are each individually the same or different and arean alkyl, aryl, aralkyl, alkaryl, haloalkyl, haloaryl, haloaralkyl, ortogether form a heterocyclic or cycloalkyl ring; and R³ is alkyl, aryl,aralkyl or alkaryl. Preferably, M is Mo; X is O; R¹ is phenyl orphenyl-(R⁵) wherein R⁵ is phenyl, isopropyl or alkyl; R is —C(CH₃)₃,—C(CH₃)(CF₃)₂,

[0086] (wherein R⁴ is phenyl, naphthyl, binaphtholate or biphenolate);and R³ is —C(CH₃)₂C₆H₅. Particularly preferred are2,6-diisopropylphenylimidoneophylidene molybdenum (VI) bis(hexafluoro-t-butoxide) (designated herein as “MoHFTB ”) and2,6-diisopropylphenylimidoneophylidene molybdenum (VI) bis(t-butoxide)(designated herein as “MoTB”). Such molybdenum catalysts are describedin Bazan, G. C., Oskam, J. H., Cho, H. N., Park, L. Y., Schrock, R. R.,Journal of the American Chemical Society, 1991, 113, 6899 and U.S. Pat.No. 4,727,215. Alexander, B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.;Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041; Zhu, S.; Cefalo, D.R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock,R. R. J. Am. Chem. Soc. 1999,121, 8251; and Aeilts, S. L.; Cefalo, D.R.; Bonitatebus, Jr., P. J.; Houser, J. H.; Hoveyda, A. H.; Schrock, R.R. Angew. Chem. Int. Ed. 2001, 40, 1452. Illustrative examples are givenbelow:

[0087] The catalyst can be delivered at the surface of the substrate byany deposition or incorporation method. Typically the catalyst isapplied in a liquid composition to the substrate surface. The catalystin its substantially pure form may exist as a liquid or solid at normalambient conditions. If the catalyst exists as a liquid, it may be mixedwith a carrier fluid in order to dilute the concentration of thecatalyst. If the catalyst exists as a solid, it may be mixed with acarrier fluid so that it can be easily delivered to the substratesurface. Of course, a solid catalyst may be applied to the surfacewithout the use of a liquid carrier fluid. The preferredRuCl₂(PCy₃)₂═CHPh, homobimetallic ruthenium, MoHFTB and MoTB catalystsexist as solids at normal ambient conditions and thus are usually mixedwith carrier fluids. The catalyst composition could also be considered aprimer in the sense that it primes the substrate surface for subsequentapplication of a coating or an adhesive.

[0088] Alternatively, the catalyst may also be mixed in bulk with thesubstrate material. If the catalyst is mixed in bulk with the substratematerial, it is preferably exuded or “bled” towards the surface of thesubstrate. One method for making such a catalyst-containing substrate isto mix the catalyst in bulk with the substrate material and then formthe resulting mixture into the substrate article via molding, extrusionand the like. Of course, the catalyst cannot be deactivated by thecomposition of the substrate material or by the method for making thesubstrate article.

[0089] The present invention preferably does not require anypre-functionalization of the substrate surface prior to application ofthe catalyst. In other words, the substrate surface does not have to bereacted with any agent that prepares the surface for receiving thecatalyst. For example, formation on the substrate surface of a so-calledmonolayer or self-assembling layer made from a material (such as athiol) different than the catalyst or the metathesizable adhesive orcoating is unnecessary. The catalyst can be applied to be in “directcontact” with the substrate surface. Of course, for metallic substratesthe substrate surface can be pre-treated with conventional cleaningtreatments or conversion treatments and for elastomer substrates thesurface can be solvent-wiped.

[0090] The catalyst may be dispersed, suspended or dissolved in thecarrier fluid. The carrier fluid may be water or any conventionalorganic solvent such as dichloroethane, toluene, methyl ethyl ketone,acetone, tetrahydrofuran, N-methyl pyrrolidone,3-methyl-2-oxazolidinone, 1,3-dimethylethyleneurea,1,3-dimethylpropyleneurea and supercritical carbon dioxide. Ruthenium,osmium and iridium catalysts are particularly useful in polar organicand aqueous carrier systems. The carrier fluid can be capable ofevaporating from the substrate surface under normal ambient conditionsor upon heating.

[0091] The amount of catalyst applied to the substrate should besufficient to effect the metathesis polymerization. The amount variesdepending upon a variety of factors including substrate type and desiredproperties but it could range from 0.001 to 10, preferably, 0.01 to 5and more preferably 0.1 to 5 mg/cm² substrate surface area.

[0092] The adhesive or coating of the invention offers numerousease-of-use advantages. The metathesis polymerization occurs undernormal ambient conditions in air regardless of whether moisture ispresent. There is no need for an exterior energy source such asradiation, thermal or photochemical for curing to produce the adhesiveor coating. Thus, the adhesive or coating will adhere to thermally orsolvent sensitive surfaces. In addition, there are a minimal number ofsteps according to the invention. There is no need to initially reactthe substrate surface to form any particular type of functional groupson the surface. There is no need for multiple, carefully controlledsteps required for forming so-called monolayers or self-assemblinglayers. The bond formed by the method of the invention displaysremarkable adhesive strength considering the ease-of-use of the method.

[0093] A further significant advantage is that the method of theinvention is environmentally-friendly. The catalyst can be delivered tothe substrate surface with an aqueous carrier fluid. Substantially pureor technical grade metathesizable monomer/oligomer can be used and themonomer/oligomer is substantially 100% reactive. Consequently, there aresubstantially no volatile organic solvents used according to oneembodiment of the invention.

[0094] Although not bound by any theory, it is believed that theadhesive or coating formed according to the invention achieves itsremarkable bonding due to a number of factors. The monomer and/orcatalyst diffuses readily into the substrate surface, particularlyelastomeric substrates. As a result of this diffusion, aninterpenetrating network develops between the polymer chains formed fromthe metathesizable material and molecular structure of the substratematerial. Moreover, the metathesis polymerization reaction may well alsoencourage the formation of strong covalent bonds formed betweenmolecules of the metathesizable material and molecules of the substrate.A unique advantage of the coating is its excellent adherence to thesubstrate surface.

[0095] The adhesive or coating is an addition polymer formed via themetathesis reaction. The resulting polymer should be capable of forminga continuous film. Olefin metathesis typically yields polymers having anunsaturated linear backbone. The degree of unsaturation functionality ofthe repeat backbone unit of the polymer is the same as that of themonomer. With a norbornene reactant, the resulting polymer should have astructure represented by:

[0096] wherein n can be 1 to 20,000, preferably 1 to 500, morepreferably 1 to 100, and most preferably 10 to 100. The molar ratio ofnorbornene reactant to catalyst should range from 20,000:1 to 1:1,preferably 500:1 to 1:1, and most preferably 100:1 to 10:1.

[0097] The resulting polymer film can be brittle, but surprisinglysuperior bonding occurs even with flexible substrates. It appears thatany cracking of the film does not propagate into the substrate.

[0098] According to a preferred embodiment of the invention the liquidcatalyst (either by itself or as a component of a multi-componentcatalyst composition) is applied to the substrate surface. The catalystcan be applied to achieve continuous surface coverage or coverage onlyin predetermined selected areas by any conventional coating/printingmeans such as spraying, dipping, brushing, wiping, roll-coating or thelike. The metathesizable material can be contacted with the resultingcatalyzed-coated surface when it is still wet. However, the catalystcarrier fluid preferably is allowed to evaporate and then themetathesizable material is applied to the dry catalyzed-coated surface.Evaporation of the catalyst carrier fluid can occur over time in normalambient conditions or it can be accelerated by subjecting thecatalyst-coated surface to heat or vacuum. A noteworthy advantage of theinvention is that the dry catalyst-coated surface remains stable andactive for an extended period of time. Although not wishing to be boundby specific limits, it is believed that the dry catalyst-coated surfaceshould retain its activity for at least five minutes, preferably atleast 24 hours, more preferably for at least 1 month, and mostpreferably for at least 6 months. This stability contributes tomanufacturing flexibility by providing a relatively long time periodduring which the metathesizable material may be contacted with thecatalyzed surface. For example, a series of substrates can be coatedwith the catalyst and then stored until needed for coating or bonding.In an alternative embodiment, the catalyst and the metathesizablematerial can be simultaneously spray applied to the substrate surface.

[0099] Once the catalyst has been made available at the substratesurface, the metathesizable material (whether in the form of a secondsubstrate, coating or adhesive) is brought into contact with thecatalyst on the substrate surface. The metathesizable material typicallybegins to react upon contact with the catalyst. Film formation is causedby the metathesis polymerization of the metathesizable material to forma substantially linear polymer. The film-forming rate could beaccelerated by addition of either Brønsted acids, Lewis acids or CuCl toeither the catalyst composition or the metathesizable composition.Methods for contacting the metathesizable material to thecatalyst-coated substrate surface depend upon the intended application.

[0100] If the metathesizable material is itself intended to form acoating, then it can be applied in a liquid form under normal ambientconditions to the catalyst-coated substrate surface by any conventionalcoating/printing means such as spraying, dipping, brushing, wiping,roll-coating or the like. The metathesizable coating material also couldbe applied by extrusion if it is in the form of a molten material. Thecoating thickness can be varied according to intended use.

[0101] The metathesizable material, especially in the form of a monomer,can be included as a component in a multi-component exterior coatingformulation such as a paint or caulk. In such a system the catalystcould be included in a primer formulation that is applied prior to theexterior coating.

[0102] If the metathesizable material is intended to form an adhesivefor adhering two substrates together, the metathesizable material can beapplied in a liquid form under normal ambient conditions directly to thecatalyst-coated substrate surface by any conventional coating/printingmeans such as spraying, dipping, brushing, wiping, roll-coating or thelike. The other substrate surface then is brought into contact with themetathesizable material before curing of metathesizable material iscomplete. Preferably, however, the metathesizable material is applied tothe substrate surface that is not coated with the catalyst and themetathesizable adhesive-coated substrate and the catalyst-coatedsubstrate can be brought into contact under normal ambient conditions toeffect the adhesive bonding. The metathesizable material can be appliedin a liquid form under normal ambient conditions directly to thenon-catalyst-coated substrate surface by any conventionalcoating/printing means such as spraying, dipping, brushing, wiping,roll-coating or the like. The metathesizable material can be allowed todry or remain wet prior to bringing the two substrates together. Themetathesizable adhesive material also could be applied in both of thesealternative methods by extrusion if it is in the form of a moltenmaterial. If the metathesizable material is a solid at room temperature,then it should be heated to at least partially melt or become asemi-solid in order to facilitate bonding. Pressure also could beapplied to a solid metathesizable material to achieve a micro liquidsurface layer.

[0103] The types of substrate surfaces that can be coated or bondedaccording to the invention vary widely. The substrates, of course, arearticles of manufacture that are themselves useful. Such substratescould include machined parts made from metal and elastomers, moldedarticles made from elastomers or engineering plastics, extruded articlessuch as fibers or parts made from thermoplastics or thermosets, sheet orcoil metal goods, fiberglass, wood, paper, ceramics, glass and the like.As used herein “substrate” does not include conventional catalystsupports made from bulk materials such as alumina or silica.Conventional catalyst supports are useful only to support a catalyst toeffect polymerization, but would not be useful by themselves without thecatalyst.

[0104] Illustrative elastomer substrates include natural rubber orsynthetic rubber such as polychloroprene, polybutadiene, polyisoprene,styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymerrubber (“NBR”), ethylene-propylene copolymer rubber (“EPM”),ethylene-propylene-diene terpolymer rubber (“EPDM”), butyl rubber,brominated butyl rubber, alkylated chlorosulfonated polyethylene rubber,hydrogenated nitrile rubber (“HNBR”), silicone rubber, fluorosiliconerubber, poly(n-butyl acrylate), thermoplastic elastomer and the like aswell as mixtures thereof.

[0105] Illustrative engineering plastic substrates useful in theinvention include polyester, polyolefin, polyamide, polyimide,polynitrile, polycarbonate, acrylic, acetal, polyketone, polyarylate,polybenzimidazoles, polyvinyl alcohol, ionomer, polyphenyleneoxide,polyphenylenesulfide, polyaryl sulfone, styrenic, polysulfone,polyurethane, polyvinyl chloride, epoxy and polyether ketones.

[0106] Illustrative metal substrates include iron, steel (includingstainless steel and electrogalvanized steel), lead, aluminum, copper,brass, bronze, MONEL metal alloy, nickel, zinc, tin, gold, silver,platinum, palladium and the like. Prior to application of the catalystaccording to the invention the metal surface can be cleaned pursuant toone or more methods known in the art such as degreasing andgrit-blasting and/or the metal surface can be converted or coated viaphosphatizing, electrodeposition, or autodeposition.

[0107] Illustrative fiber substrates include fiberglass, polyester,polyamide (both nylon and aramid), polyethylene, polypropylene, carbon,rayon and cotton.

[0108] Illustrative fiber-reinforced or -impregnated compositesubstrates include fiberglass-reinforced prepreg (“FRP”), sheet moldingcompound (“SMC”) and fiber-reinforced elastomer composites. In the caseof fiber-reinforced elastomer composites, fiber substrates can besandwiched between and bonded to outer elastomer layers to form acomposite multilayer composite structure such as tires, belts for theautomotive industry, hoses, air springs and the like. The metathesizableadhesive of the invention could be used to bond fiber reinforcing cordto tire materials.

[0109] The adhesive embodiment of the invention could also be used tomake fiber-reinforced or -impregnated composites themselves. Forexample, the catalyst can be applied to the fiber or cord and theneither a separate metathesizable material is contacted with thecatalyst-treated fiber or cord so as to form an adhesive with thecomposite matrix material or the composite matrix material is itselfmetathesizable.

[0110] The invention is particularly useful to adhere two substrates toeach other. The types of substrates mentioned above could all be bondedtogether according to the invention. The substrates can each be madefrom the same material or from different materials. The invention isespecially useful in bonding post-vulcanized or cured elastomer,particularly to a substrate made from a different material such asmetal.

[0111] It has been found that superior bonding of cured elastomersubstrates is obtained if the metathesizable material is applied to thecured elastomer substrate surface and then the adhesive-appliedelastomer substrate is contacted with the catalyst-coated othersubstrate. This procedure is shown schematically in FIG. 1. Thispreferred method is especially applicable to bonding cured elastomer tometal and cured elastomer to cured elastomer. The catalyst is applied tothe surface of the metal substrate and allowed to dry. Themetathesizable adhesive is applied to the surface of the elastomersubstrate. The catalyst-coated metal substrate and the adhesive-appliedsubstrate are brought together under minimal pressure that is adequatesimply to hold the substrates together and in place until the metathesisreaction initiated by contact with the catalyst has progressed to thepoint of curing sufficient to provide at least a “green strength” bond.Depending upon the rate of diffusion of metathesizable material into thesubstrate and the rate of evaporation of the metathesizable material,there may be a lapse of up to 30 minutes before the two substrates arebrought together, but preferably the lapse is about 30 seconds to about5 minutes. In the case of bonding cured EPDM to steel, green strengthappears to develop within approximately five to ten minutes after thesubstrates are contacted together and sufficiently high bond strengthappears to develop within approximately thirty minutes after thesubstrates are contacted together.

[0112] The bonding process of the invention is particularly useful forbonding a substrate made from a thermoplastic elastomer such asSANTOPRENE® to another thermoplastic elastomer substrate or to asubstrate made from a different material. SANTOPRENE® is the tradedesignation of a thermoplastic elastomer (“TPE”) commercially availablefrom Advanced Elastomer Systems that consists of elastomer particlesdispersed throughout a continuous matrix of thermoplastic material. SuchTPE blends are described in detail in U.S. Pat. No. 5,609,962,incorporated herein by reference. As used herein, TPE also includesthermoplastic olefins (“TPO”) such as those described in U.S. Pat. No.5,073,597, incorporated herein by reference.

[0113] TPE's are well known. Many TPE's contain principally polyolefin,susch as a blend of polypropylene homopolymer and a copolymer ofpropylene with another α-olefin like 1-octene. According to the '962patent monoolefin monomers having 2 to 7 carbon atoms are suitable, suchas ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene,1-octene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene,mixtures thereof and copolymers thereof with (meth)acrylates and/orvinyl acetates. Preferred TPE's are made from monomers having 3 to 6carbon atoms, with propylene being preferred. The polypropylene can behighly crystalline isotactic or syndiotactic polypropylene.

[0114] A portion of the polyolefin component in a TPE can be afunctionalized polyolefin according to the '962 patent. In other words,non-functionalized polyolefins and functionalized polyolefins can beblended or mixed together to form the TPE. The polyolefins of thefunctionalized polyolefins can be homopolymers of alpha-olefins such asethylene, propylene, 1-butene, 1-hexene and 4-methyl-1-pentene andcopolymers of ethylene with one or more alpha-olefins. Preferable amongthe polyolefins are low-density polyethylene, linear low-densitypolyethylene, medium- and high-density polyethylene, polypropylene, andpropylene-ethylene random or block copolymers. The functionalizedpolyolefins contain one or more functional groups which have beenincorporated during polymerization. However, they are preferablypolymers onto which the functional groups have been grafted. Suchfunctional group-forming monomers are preferably carboxylic acids,dicarboxylic acids or their derivatives such as their anhydrides.

[0115] The elastomer component of TPE is made from olefinic rubbers suchas EPM, EPDM, butyl rubber, copolymer of a C₄₋₇ isomonoolefin and apara-alkylstyrene, natural rubber, synthetic polyisoprene,polybutadiene, styrene-butadiene copolymer rubber, nitrile rubber,polychloroprene and mixtures thereof.

[0116] According to the '962 patent, the amount of polyolefin isgenerally from about 10 to about 87 weight percent, the amount of rubberis generally from about 10 to about 70 weight percent, and the amount ofthe functionalized polyolefin is about 3 to about 80 weight percent,provided that the total amount of polyolefin, rubber and functionalizedpolyolefin is at least about 35 weight percent, based on the totalweight of the polyolefin, rubber, functionalized polyolefin and optionaladditives.

[0117] The olefin rubber component is generally present as small, e.g.,micro-size, particles within a continuous polyolefin matrix. The rubberis partially crosslinked (cured) and preferably fully crosslinked orcured. The partial or full crosslinking can be achieved by adding anappropriate rubber curative to the blend of polyolefin and rubber andvulcanizing the rubber to the desired degree under conventionalvulcanizing conditions. It is preferred that the rubber be crosslinkedby the process of dynamic vulcanization wherein the rubber is vulcanizedunder conditions of high shear at a temperature above the melting pointof the polyolefin component. The rubber is thus simultaneouslycrosslinked and dispersed as fine particles within the polyolefinmatrix.

[0118] The bonding method of the invention is also particularly usefulfor bonding an elastomeric or plastic tire tread to an elastomeric orplastic tire carcass. As described above, tire tread replacement orretreading generally involves adhering a pre-cured or uncured retreadstock directly to a cured tire carcass. The metathesizable adhesivematerial of the invention can be used to replace the adhesive cushion orcushion gum layer currently used in the retreading art.

[0119] The metathesis catalyst is applied to a bonding surface of eitherthe tire carcass or a bonding surface of the tire tread and themetathesizable material is applied to the other bonding surface of thetire carcass or tire tread. Preferably, the catalyst is applied to thetire carcass and the metathesizable material is applied to the tiretread. The carcass of the used tire can be buffed by known means toprovide a surface for receiving the catalyst or metathesizable material.It is preferred that the bonding surface is mildly rough or only lightlysanded. The catalyst or metathesizable material-coated retread stock isplaced circumferentially around the catalyst or metathesizable-coatedtire carcass. The coated surfaces then are contacted together withminimal pressure sufficient simply to hold the tread and carcasstogether. The tread stock and carcass can be held together during curingof the metathesis material by any conventional means in the retread artsuch as stapling or placing a cover or film around the tire assembly.Curing is initiated when the surfaces are contacted, green strengthbegins to develop within approximately five to ten minutes, and highbond strength begins to develop within approximately 15 minutes to onehour.

[0120] The resulting tire laminate includes a tire carcass or casing, atire retread and a metathesis polymer adhesive layer between the carcassand retread. The tire laminate is useful for various types of vehicletires such as passenger car tires, light and medium truck tires,off-the-road tires, and the like. This bonding process is alsoapplicable to the manufacture of new tires wherein a tread is applied toa treadles tire casing or carcass. The catalyst and metathesizablematerial typically are applied in liquid form.

[0121] Retread or tread stock is well known in the art and can be anycured or uncured conventional synthetic or natural rubber such asrubbers made from conjugated dienes having from 4 to 10 carbon atoms,rubbers made from conjugated diene monomers having from 4 to 10 carbonatoms with vinyl substituted aromatic monomers having from 8 to 12carbon atoms, and blends thereof. Such rubbers generally contain variousantioxidants, fillers such as carbon black, oils, sulfur, accelerators,stearic acid, and antiozonants and other additives. Retread or treadstock can be in the form of a strip that is placed around the outerperiphery of the concentric circular tire carcass or casing. The curedcarcass is similarly well known in the art and is made from conjugateddienes such as polyisoprene or natural rubber, rubbers made fromconjugated diene monomers having from 4 to 10 carbon atoms with vinylsubstituted aromatic monomers having from 8 to 12 carbon atoms, andblends thereof. Such rubbers generally contain various antioxidants,fillers such as carbon black, oils, sulfur, accelerators, stearic acid,and antiozonants and other additives.

[0122] The invention will be described in more detail by way of thefollowing non-limiting examples. Unless otherwise indicated, the steelcoupons used in the examples are made from grit-blasted, 1010 fullyhardened, cold rolled steel, the cured EPDM rubber strips are availablefrom British Tire and Rubber under the designation 96616 and all bondingand coating was performed at normal ambient conditions.

[0123] Primary adhesion of the bonded samples was tested according toASTM-D 429 Method B. The bonded samples are placed in an Instron and theelastomeric substrate is peeled away from the other substrate at anangle of 180° at 50.88 mm (2 inches) per minute. The mean load atmaximum load and the mean energy-to-break point are measured. Afterbeing pulled apart, the samples are inspected to determine the failuremode. The most desirable failure mode is rubber tear—a portion of theelastomeric material of one substrate remains on the other substrate.Rubber tear indicates that the adhesive is stronger than the elastomericmaterial.

EXAMPLE 1 Bonding of EPDM-to-Metal—Application of Catalyst by Drip orFlooding Process

[0124] A catalyst solution was prepared by dissolving 0.021 g ofRuCl₂(PCy₃)₂═CHPh in 1.5 ml of CH₂Cl₂. Three grit-blasted steel couponswere prepared by pipetting 0.5 ml of the catalyst solution via syringeonto each coupon to just cover its surface (34.9 mm×25.4 mm) and thesolvent allowed to evaporate for three to four minutes in the openlaboratory atmosphere. This gave≧7 mg of RuCl₂(PCy₃)₂═CHPh per coupon.The metal coupons were usually washed with acetone and dried prior toapplication of catalyst solution, but this was not required. In thisexample, the coupons were unwashed. EPDM rubber strips were prepared bywashing the bonding surface (34.9 mm×25.4 mm) with acetone, drying atroom temperature for 3 to 4 minutes, and then applying via syringe 0.03ml of ENB to each coupon and spreading it evenly with the needle tip.The catalyst-coated metal coupon was immediately placed on top of theENB-coated EPDM strip so that both treated surfaces contacted each otherand a weight of approximately 100 gm was placed on top of the matedarea. The samples sat at ambient conditions overnight. All the samplescould not be pulled apart by hand. They were evaluated using a 180° peeltest on an Instron and showed only EPDM rubber tear on failure. A totalof 12 samples were tested and the mean load at maximum load was 273.04(N) and the mean energy to break was 37.87 (J).

EXAMPLE 2 Bonding of EPDM-to-Metal

[0125] This testing was performed as preliminary screening to evaluatedifferent application methods for bonding EPDM-to-metal. The processdescribed in Example 1 was used to apply the RuCl₂(PCy₃)₂═CHPh catalystsolution or ENB to either a grit-blasted steel coupon or EPDM rubberstrip. The results are shown below in Table 1. Based on these results,it appears that the best bonding method occurred when the catalyst wasapplied to the metal and the ENB was applied to the EPDM. In Table 1 thesubstrate type listed under the catalyst or monomer is the substrate towhich the catalyst or monomer is applied. TABLE 1 Comparison Bondingbetween Application Surfaces Catalyst Monomer Bond Notes metal rubbergood Could not pull apart by hand in tension. Metal^(a) metal^(a)variable One sample pulled apart while the other two could not be pulledapart totally and showed rubber tear. Metal^(a) metal^(a) variable Freshcatalyst soln used. One sample pulled apart while the other two couldnot be pulled apart totally and showed rubber tear. Rubber metal poorAdhesion to rubber was good, poor to metal. Rubber^(b) rubber^(b) poorAdhesion to rubber was good, poor to metal. Rubber^(b) rubber^(b) poorFresh catalyst soln used. Adhesion to rubber was good, poor to metal.

EXAMPLE 3 Delayed Bonding of Substrates Coated with Catalyst

[0126] A catalyst solution was applied to grit-blasted metal couponsaccording to the process described in Example 1, but the catalyst-coatedcoupons were allowed to dry and stand in ambient conditions in thelaboratory (except for being covered from dust) for 3, 10, 20 and 33days before bonding to the EPDM with ENB. All samples showed EPDM rubbertear when subjected to the 180° peel test. The 3 day samples had a meanload at maximum load of 291.49 (N) and a mean energy to break of 39.29(J); 10 day samples had a mean load at maximum load of 298.32 (N) and amean energy to break of 40.18 (J); 20 day samples had a mean load atmaximum load of 262.79 (N) and a mean energy to break of 35.76 (J); andthe 33 day samples had a mean load at maximum load of 313.26 (N) and amean energy to break of 48.48 (J).

EXAMPLE 4 Application of Catalyst to Substrate by Brush Process

[0127] A catalyst solution was prepared by dissolving 0.021 g ofRuCl₂(PCy₃)₂═CHPh to 1.5 ml of CH₂Cl₂ in a screw-cap vial under N₂. Thissolution was applied by brush to three grit-blasted steel coupons overthe surface to be bonded (34.9 mm×25.4 mm) and the solvent allowed toevaporate in the open laboratory atmosphere during the brushing process,thus leaving the catalyst powder evenly distributed over the metalcoupon surface. After drying, all prepared samples were weighed todetermine the amount of catalyst on the surface which was 5.8±1.8 mg percoupon. When the first-made solution was depleted, another batch offresh catalyst solution was prepared as described above. A total of 12samples were prepared in this manner. EPDM rubber strips were preparedby washing the bonding surface (34.9 mm×25.4 mm) with acetone, drying atroom temperature for 3 to 4 minutes, and then applying via syringe 0.03ml of ENB to each coupon and spreading it evenly with the needle tip.The catalyst-coated metal coupon was immediately placed on top of theENB-coated EPDM strip so that both treated surfaces contacted each otherand a weight of approximately 100 gm was placed on top of the matedarea. The samples sat at ambient conditions overnight. The next morning,no failure was observed on attempted pulling the samples apart by hand.They were evaluated using a 180° peel test on an Instron and showedevenly distributed rubber tear on the EPDM on failure. A total of 12specimens were tested and showed a mean load at maximum load of 283.87(N) and mean energy to break of 41.72 (J).

EXAMPLE 5 Application of Waterborne Catalyst to Substrate

[0128] A catalyst solution was prepared by dissolving 0.015 g ofRuCl₂(PCy₃)₂═CHPh and 0.006 g of dodecyltrimethylammonium bromide(“DTAB”) surfactant (0.488 w/w %) in 1.21 g of water. The aqueouscatalyst solution was brushed onto two grit-blasted metal coupons usingthe procedure described in Example 4 except that the coupons were heatedon a hot-plate at 40° C. to aid in water removal. The coupons werecooled to room temperature and bonded to EPDM with 0.04 ml of ENB asdescribed in Example 4. The next morning the samples could be pulledapart by hand.

[0129] In another example, a catalyst solution was prepared from 0.0272g of RuCl₂(PCy₃)₂═CHPh and 0.0024 g of DTAB (0.068 w/w %) in 3.5 g ofwater. The aqueous catalyst solution was brushed onto three grit-blastedmetal coupons as described above, cooled to room temperature, and bondedto EPDM with 0.04 ml of ENB as described in Example 4. They wereevaluated using a 180° peel test on an Instron and showed rubber tear onthe EPDM on failure. A total of three specimens were tested and showed amean load at maximum load of 215.07 (N) and mean energy to break of23.09 (J).

EXAMPLE 6 ENB Monomer Residence Time on EPDM Substrate

[0130] Bonding of EPDM to grit-blasted steel coupons was performedaccording to Example 1 except that 0.04 ml of ENB was allowed to standon the EPDM surface to be bonded for 0, 2, and 4 minutes before bondingto the metal. For the 4 minute sample, an additional 0.03 ml of ENB wasapplied onto two of the EPDM strips since the liquid absorbed into theEPDM. All samples exhibited EPDM rubber tear when subjected to the 180°peel test. The 0 minute samples had a mean load at maximum load of256.41 (N) and a mean energy to break of 29.45 (J); 2 minutes sampleshad a mean load at maximum load of 273.12 (N) and a mean energy to breakof 35.34 (J); and the 4 minutes samples had a mean load at maximum loadof 247.28 (N) and a mean energy to break of 22.82 (J).

EXAMPLE 7 EPDM-to-Metal Bonding Using Different Steel Substrates

[0131] Phosphatized and unprocessed 1010 steel were bonded to EPDMrubber according to the procedure described in Example 1. Bondingstrength was reduced compared to grit-blasted steel, but all the samplesstill exhibited some EPDM rubber tear when subjected to the 180° peelstrength test. The phosphatized steel samples had a mean load at maximumload of 158.69 (N) and a mean energy to break of 13.49 (J); and theunprocessed 1010 steel samples had a mean load at maximum load of 209.07(N) and a mean energy to break of 19.88 (J).

EXAMPLE 8 Application of Catalyst to Substrate by Spray Process

[0132] A catalyst solution was prepared by dissolving 0.5 g ofRuCl₂(PCy₃)₂═CHPh in 20 ml of CH₂Cl₂. The catalyst solution was sprayedonto 12 grit-blasted steel coupons in a sweeping pattern untileven-appearing coverage of the surface to be bonded (34.9 mm×25.4 mm)was obtained. The solvent was allowed to evaporate for 1.5 hours in theopen laboratory atmosphere. After drying, all prepared samples wereweighed to determine the amount of catalyst on the surface, which was9.0±0.95 mg per coupon. EPDM rubber strips were prepared by washing thebonding surface (34.9 mm×25.4 mm) with acetone, drying at roomtemperature for 3 to 4 minutes, and then applying via syringe 0.06 ml ofENB to each coupon and spreading it evenly with the needle tip. Thecatalyst-coated metal coupon was immediately placed on top of theENB-coated EPDM strip so that both treated surfaces contacted each otherand a weight of approximately 100 g was placed on top of the mated area.The samples sat at ambient conditions overnight. The next morning, allsamples could not be pulled apart by hand and showed only EPDM rubbertear after analysis on an Instron. A total of 12 samples were tested anddisplayed a mean load at maximum load of 352.47 (N) and a mean energy tobreak of 61.23 (J).

EXAMPLE 9 EPDM-to-Metal Bonding Using Other Metals

[0133] A catalyst solution was prepared by dissolving 0.030 g ofRuCl₂(PCy₃)₂═CHPh in 2.5 ml of CH₂Cl₂. The catalyst solution was appliedto steel Q-panel, aluminum, and chromated aluminum metal coupons and themetal coupons were bonded to EPDM rubber strips with 0.04 ml of ENBmonomer per coupon as described in Example 4. Three separate butidentical batches of catalyst solution were used to prepare the metalcoupons, which resulted in 7.3±1.2 mg catalyst per coupon afterweighing. The specimens were analyzed on an Instron with a 180° peeltest. All three metals showed a very small amount of rubber tear withadhesive failure as the primary failure mode as most of the ENB polymerfilm was attached to the rubber on failure. Higher bond strengths wereobserved with the chromated aluminum surfaces. TABLE 2 180° Peel TestData for EPDM-to-Steel, -Aluminum, and -Chromated Aluminum Specimens.Sample Type Load at Max. Load (N) Energy to Break (J) Steel Q-Panel81.08 3.91 Steel Q-Panel 87.08 3.78 Steel Q-Panel 79.95 3.04 Mean 82.713.58 Al 84.45 3.59 Al 82.03 4.37 Al 114.25 6.33 Mean 93.58 4.76 chrom.Al 173.28 13.00 chrom. Al 113.86 6.88 chrom. Al 144.55 8.54 Mean 143.899.47

EXAMPLE 10 Santoprene®-to-Metal Bonding Examples

[0134] A catalyst solution was prepared by dissolving 0.030 g ofRuCl₂(PCy₃)₂═CHPh in 3.0 ml of CH₂Cl₂. The catalyst solution was appliedto grit-blasted steel coupons and the steel coupons were bonded to threesamples of four types of Santoprene® (101-64, 201-64, 201-87 and8201-90) with 0.08 ml of ENB monomer per coupon as described in Example4. Weighing revealed on average that 9.4±1.2 mg of catalyst wascontained per coupon. The rubber surface was sanded prior to applicationof monomer for each type. The bonded specimens were analyzed on theInstron with the 180° peel test and the results are shown below in Table3. All three samples of both softer rubbers, 101-64 and 201-64, showedexcellent rubber tear while the stiffer rubbers, 201-87 and 8201-90,showed no rubber tear and adhesive failure was prominent with most ofthe ENB polymer film attached to the rubber after peeling thesespecimens apart. Good bond strength data were observed for allspecimens. TABLE 3 180° Peel Test Data for Rubber-to-Metal Bonded SandedSantoprene ® Specimens. Sample Type Load at Max. Load (N) Energy toBreak (J) 101-64 106.60 2.49 101-64 98.75 5.60 101-64 105.32 2.25 Mean103.56 3.45 201-87 72.76 3.69 201-87 87.64 3.27 201-87 103.56 3.96 Mean87.99 3.64 201-64 72.45 4.09 201-64 114.54 3.30 201-64 90.27 5.41 Mean92.42 4.27 8201-90  165.54 4.35 8201-90  165.24 6.02 8201-90  230.068.54 Mean 186.94 6.30

EXAMPLE 11 Natural Rubber-to-Grit-Blasted Steel Bonding

[0135] RuCl₂(PCy₃)₂═CHPh was applied to grit-blasted steel coupons andbonded with 0.10 ml of ENB monomer per coupon using the processdescribed in Example 4. Four natural rubber samples were prepared. Twosamples were sanded and two samples remained unsanded. The matedspecimens were allowed sit over a two day period. On the third day, thetwo specimens prepared from the sanded natural rubber pulled apart byhand. A thin ENB polymer film was left on the natural rubber strip andsome rubber tear was observed. The two specimens prepared from unsandednatural rubber could not be pulled apart by hand and were analyzed onthe Instron using a 180° peel test. The bonded specimens had a mean loadat maximum load of 183.14 (N) and a mean energy to break of 12.20 (J).Rubber tear was observed for the sample with the higher values.

EXAMPLE 12 EPDM-to-Grit-Blasted Steel Bonding with MoTB Catalyst

[0136] A catalyst solution was prepared by dissolving 0.021 g of2,6-diisopropyl-phenylimido neophylidene molybdenum (VI) bis-t-butoxide(MoTB) in 2 ml of CH₂Cl₂. The catalyst solution was applied togrit-blasted steel coupons and then the steel coupons were bonded toEPDM rubber strips with 0.08-0.09 ml of ENB monomer per coupon asdescribed in Example 4. Because of catalyst sensitivity to air andmoisture, all handling of rubber and metal coupons and catalystsolutions was performed in a glove box under an argon atmosphere. Oncebonded, the samples were kept in the glove box until mechanical testswere performed. The original grit-blasted metal and rubber coupons hadbeen stored in the glove box for several months to ensure completeremoval of any water or oxygen contamination. This was later found to beunnecessary as bonding was observed even with samples that had only afew hours residence time in the glove box. It was noted that within 5-10seconds after mating the two surfaces, the coupons could not be movedaround on top of each other suggesting that polymerization had occurred.All specimens were analyzed on an Instron using the 180° peel test. Theresults are means for two separate data sets: the original two bondedspecimens (long residence time in the glove box)—mean load at maximumload of 46.57 (N) and mean energy to break of 1.54 (J) and three newspecimens (surfaces were thoroughly washed with acetone prior to placingin the glove box followed by washing with CH₂Cl₂ in the box prior toaddition of monomer) —mean load at maximum load of 139.26 (N) and meanenergy to break of 11.12 (J). Some rubber tear was observed on allspecimens except one.

EXAMPLE 13 EPDM-to-Grit-Blasted Steel Bonding using HomobimetallicRuthenium Catalyst.

[0137] A catalyst solution was prepared by dissolving 0.030 g ofRuCl₂(p-cymene)-RUCl₂(PCy₃)₂═CHPh in 3.1 ml of CH₂Cl₂. The catalystsolution was applied to grit-blasted steel coupons and then the steelcoupons were bonded to EPDM rubber strips with 0.08 ml of ENB monomerper coupon as described in Example 4. The mated specimens were analyzedon the Instron using a 180° peel test. The bonded specimens had a meanload at maximum load of 226.60 (N) and a mean energy to break of 26.78(J). Rubber tear was observed for all specimens.

EXAMPLE 14 EPDM-to-Grit-Blasted Steel Bonding using DCPD as Monomer

[0138] A catalyst solution was prepared by dissolving 0.031 g ofRuCl₂(PCy₃)₂=CHPh in 3.2 ml of CH₂Cl₂. The catalyst solution was appliedto grit-blasted steel coupons and the steel coupons then were bonded toEPDM rubber strips with DCPD monomer as described in Example 4. Theprocedure for application of the DCPD varied slightly from that withENB. The EPDM surface was washed with acetone prior to application ofDCPD monomer, which required gentle melting of the distilleddicyclopentadiene with a heat gun, pipetting the liquid onto the EPDMsurface and spreading the liquid with a pipette. On cooling, the DCPDsolidified. Once the monomer was applied, the DCPD coated surface wasgently heated with a heat gun to melt the solid; the metal and rubberparts were immediately mated and weighted down with approximately 100grams. The mated specimens were analyzed on the Instron using a 180°peel test. The bonded specimens had a mean load at maximum load of290.78 (N) and a mean energy to break of 44.44 (J). Rubber tear wasobserved for all specimens.

EXAMPLE 15 EPDM-to-Grit-Blasted-Steel Bonding usingMethylidenenorbornene as Monomer

[0139] A catalyst solution was prepared by dissolving 0.031 g ofRuCl₂(PCy₃)₂═CHPh in 3.2 ml of CH₂Cl₂, applied to three grit-blastedsteel coupons, and then the steel coupons were bonded to EPDM with 0.10ml of methylidenenorbornene monomer per coupon as described in Example4. The mated specimens were analyzed on the Instron using a 180° peeltest. The bonded specimens had a mean load at maximum load of 40.55 (N)and a mean energy to break of 1.48 (J).

EXAMPLE 16 EPDM-to-EPDM Bonding

[0140] A catalyst solution was prepared by dissolving 0.030 g ofRuCl₂(PCy₃)₂═CHPh in 2 ml of CH₂Cl₂. The catalyst solution was appliedto two EPDM strips. Each catalyst-coated EPDM strip was bonded toanother EPDM strip with 0.02 ml of ENB monomer per strip as described inExample 1. The EPDM rubber strips were washed with acetone and allowedto dry prior to application of either catalyst solution or ENB monomer.Two strips were bonded in a lap-shear configuration surface (34.9mm×25.4 mm); examination of the specimens on the next day revealed theycould not be pulled apart by hand. They were then analyzed by a lapshear tensile test on an Instron after three months of standing atambient conditions and showed an average load at break of 419.42 (N).

[0141] A catalyst solution was prepared by dissolving 0.027 g ofRuCl₂(PCy₃)₂═CHPh in 2.5 ml of CH₂Cl₂. The catalyst solution was appliedto three EPDM strips. Each catalyst-coated EPDM strip was bonded to anEPDM strip with 0.07-0.10 ml of ENB monomer per strip as described inExample 4. The EPDM rubber strips were washed with acetone and allowedto dry prior to application of either catalyst solution or ENB monomer.Six specimens were bonded in 180° peel test mode. Three were sandedbefore bonding. All specimens bonded and could not be pulled apart byhand and were analyzed on an Instron using a 180° peel test. The sandedspecimens had a mean load at maximum load of 166.51 (N) and a meanenergy to break of 25.56 (J); and the unsanded specimens had a mean loadat maximum load of 176.16 (N) and a mean energy to break of 26.97 (J).Failure analysis showed that the sanded specimens had rubber tear butthe unsanded specimens had deeper rubber tear with chunks torn away.

EXAMPLE 17 EPDM-to-EPDM Bonding with MoTB Catalyst

[0142] Two separate catalyst solutions were prepared to self-bondunsanded and sanded EPDM specimens. The first solution was prepared bydissolving 0.0216 g of 2,6-diisopropylphenylimido neophylidenemolybdenum (VI) bis-t-butoxide (MoTB) in 2 ml of CH₂Cl₂. The catalystsolution was applied to two unsanded EPDM rubber strips that were thenbonded to EPDM rubber strips with 0.08 ml of ENB monomer per coupon asdescribed in Example 12. The second solution was prepared by dissolving0.0211 g of 2,6-diisopropylphenylimido neophylidene molybdenum (VI)bis-t-butoxide (MoTB) in 0.7 ml of CH₂Cl₂. The catalyst solution wasapplied to sanded EPDM rubber strips that were then bonded to EPDMrubber strips with 0.13 ml of ENB monomer per coupon as described inExample 12. All specimens were analyzed on an Instron using the 180°peel test. The results are means for two separate data sets: theoriginal two unsanded bonded specimens (long residence time in the glovebox)- mean load at maximum load of 9.41 (N) and mean energy to break of0.27 (J) and two new specimens (surfaces were sanded prior to placing inthe glove box followed by washing with CH₂Cl₂ in the box prior toaddition of monomer)—mean load at maximum load of 12.97 (N) and meanenergy to break of 0.76 (J). No rubber tear was observed on anyspecimen.

EXAMPLE 18 EPDM-to-EPDM Bonding using Homobimetallic Ruthenium Catalystand ENB

[0143] A catalyst solution was prepared by dissolving 0.031 g ofRuCl₂(p-cymene)-RuCl₂(PCy₃)₂═CHPh in 3.1 ml of CH₂Cl₂. The catalystsolution was applied to three EPDM rubber strips that were then bondedto EPDM rubber strips with 0.16 ml of ENB monomer per coupon asdescribed in Example 4. The mated specimens were analyzed on the Instronusing a 180° peel test. The bonded specimens had a mean load at maximumload of 126.28 (N) and a mean energy to break of 11.38 (J). Rubber tearwas observed for all specimens.

EXAMPLE 19 EPDM-to-EPDM Bonding using DCPD as Monomer

[0144] A catalyst solution was prepared by dissolving 0.031 g ofRuCl₂(PCy₃)₂═CHPh in 3.1 ml of CH₂Cl₂. The catalyst solution was appliedto three EPDM strips that were then bonded to EPDM strips with DCPDmonomer as described in Examples 4 and 14. The mated specimens wereanalyzed on the Instron using a 180° peel test. The bonded specimens hada mean load at maximum load of 181.75 (N) and a mean energy to break of26.46 (J). Rubber tear was observed for all specimens.

EXAMPLE 20 Rubber-to-Rubber Bonding Using Differently Cured Rubbers

[0145] A catalyst solution was prepared by dissolving 0.031 g ofRuCl₂(PCy₃)₂═CHPh in 3.2 ml of CH₂Cl₂. This solution was applied tothree rubber strips that were then self-bonded with ENB monomer (seeTables 4 and 5 for the amount of ENB applied to each specimen) asdescribed in Example 4. Once this catalyst solution had been depleted,another identical batch was prepared and used to bond another threespecimens. Both EPDM and natural rubber A225P strips were molded andcured to different extents of cure as shown in Tables 4 and 5. Theextent cure is shown as a percentage that was determined on a MonsantoOscillating Disk Rheometer (for example, T₉₀=time at 90% of maximumtorque). Surface pretreatment of both surface types involved washingwith acetone. The A225P was sanded while the EPDM remained unsanded. TheEPDM was cured at 100, 70 and 40% and the A225P was cured at 100, 90, 70and 40%. Instron results from the 180° peel test are shown in Tables 4(EPDM) and 5 (A225P). TABLE 4 180° Peel Test Data for Extent of CureStudy for EPDM-to-EPDM Specimens. Amount of Load at Max. Sample TypeMonomer (ml) Load (N) Energy to Break (J) 100% 0.16 178.58 24.87 100%0.16 162.50 23.44 100% 0.16 173.38 24.99 Mean 171.48 24.43  70% 0.16251.00 65.69  70% 0.16 226.94 52.32  70% 0.16 236.04 57.10 Mean 238.0758.37  40% 0.10 203.10 50.35  40% 0.13 216.24 52.99  40% 0.15 238.0163.51 Mean 219.11 55.62

[0146] All samples showed excellent rubber tear. However, no deep rubbertear was observed. The 40% EPDM samples showed better rubber tear whencompared to the 70and 100% samples. TABLE 5 180° Peel Test Data forExtent of Cure Study for A225P-to-A225P Specimens. Amount of Load atMax. Sample Type Monomer (ml) Load (N) Energy to Break (J) 100% 0.10375.01 40.07 100% 0.10 304.20 29.16 100% 0.10 396.97 46.42 Mean 358.7338.55  90% 0.16 334.60 54.27  90% 0.16 261.64 40.10  90% 0.16 285.3742.51 Mean 293.87 45.63  70% 0.16 297.73 48.58  70% 0.18 264.58 42.11 70% 0.18 310.87 51.10 Mean 291.06 47.26  40% 0.10 328.91 59.14  40%0.14 356.18 63.42  40% 0.16 420.21 76.88 Mean 368.44 66.48

[0147] The 100% A225P showed good rubber tear, and the 90, 70 and 40%A225P showed deep rubber tear. It should be noted that the 100% A225Pstrips were approximately twice as thick as those for the other threetypes of cured rubber.

EXAMPLE 21 Santoprene®-to-Santoprene® Bonding

[0148] A catalyst solution was prepared by dissolving 0.030 g ofRuCl₂(PCy₃)₂═CHPh in 2.5 ml of CH₂Cl₂. This solution was applied tothree strips of four types of Santoprene® (101-64, 201-64, 201-87 and8201-90), and self-bonded with ENB monomer as described in Example 4.The amount of ENB applied depended on the Santoprene® surface treatment:0.06 ml for unsanded and 0.16 ml for sanded specimens.

[0149] Once this catalyst solution had been depleted, another identicalbatch was prepared and used to bond another three specimens. The bondedspecimens were analyzed on an Instron with the 180° peel test and theresults are shown in Tables 6 and 7. All unsanded samples showed norubber tear and displayed adhesive failure as a polymer film wasobserved on much of the rubber surface. All three 101-64 sanded samplesshowed excellent rubber tear, two 201-64 samples showed excellent rubbertear, and both stiffer rubbers, 201-87 and 8201-90, showed no rubbertear. TABLE 6 180° Peel Test Data for Rubber-to-Rubber Using UnsandedSantoprene ® Specimens. Santoprene ® Type Load at Max. Load (N) Energyto Break (J) 201-64 9.55 0.46 201-64 6.58 0.38 201-64 5.58 0.30 Mean7.24 0.38 201-87 9.14 0.43 201-87 5.45 0.27 201-87 3.39 0.19 Mean 5.990.30 101-64 4.39 0.29 101-64 7.98 0.43 101-64 7.79 0.30 Mean 6.72 0.348201-90  7.16 0.14 8201-90  3.68 0.17 8201-90  3.00 0.15 Mean 4.62 0.15

[0150] TABLE 7 180° Peel Test Data for Rubber-to-Rubber Using SandedSantoprene ® Specimens. Santoprene ® Type Load at Max. Load (N) Energyto Break (J) 101-64 85.49 3.38 101-64 93.01 3.11 101-64 58.47 3.59 Mean78.99 3.36 201-64 48.52 2.61 201-64 107.29 4.29 201-64 60.50 3.40 Mean72.10 3.43 201-87 67.95 4.00 201-87 63.76 4.03 201-87 73.98 4.36 Mean68.56 4.13 8201-90  29.85 1.69 8201-90  31.91 1.81 8201-90  21.82 1.28Mean 27.86 1.60

EXAMPLE 22 Tire Retread Applications

[0151] A catalyst solution was prepared by dissolving 0.031 g ofRuCl₂(PCy₃)₂═CHPh in 3.1 ml of CH₂Cl₂. Three types of bonding wereperformed: (1) tread-to-tread (2) carcass-to-carcass and (3)carcass-to-tread. For carcass-to-tread specimens, the catalyst wasapplied to the carcass and ENB monomer to the tread. The bondingprocedure was as described in Example 4. Once the catalyst solution hadbeen depleted another identical batch was prepared. The amount of ENBapplied depended on the specimen and is shown in Tables 8 and 9.Mechanical properties were obtained on both unsanded and sandedcombinations of carcass and tread stock. The bonded specimens wereanalyzed on an Instron with the 180° peel test. Table 8 shows data forthe unsanded specimens. All unsanded samples showed rubber tear. Thetread-to-tread samples showed some superficial rubber tear. Thecarcass-to-carcass and carcass-to-tread samples showed deep rubber tear.TABLE 8 180° Peel Test Data for Rubber-to-Rubber Bonding Using UnsandedCarcass and Tread Stocks. Amount of Load at Max. Sample Type Monomer(ml) Load (N) Energy to Break (J) Tread/Tread 0.06 72.84 6.08Tread/Tread 0.06 60.79 4.90 Tread/Tread 0.08 71.18 7.73 Mean 68.45 6.24Carcass/Carcass 0.10 261.83 36.81 Carcass/Carcass 0.14 205.64 20.79Carcass/Carcass 0.16 349.31 48.82 Mean 272.27 35.47 Carcass/Tread 0.06186.91 29.43 Carcass/Tread 0.08 134.94 17.99 Carcass/Tread 0.10 140.1416.36 Mean 154.00 21.26

[0152] Table 9 shows data for sanded specimens. These all showed rubbertear as well. However, rubber tear was deeper when compared to theunsanded specimens. The tread-to-tread samples showed the least amountof tear but still more than the unsanded version. The carcass-to-carcasssamples showed excellent, deep rubber tear. Finally, thecarcass-to-tread samples also showed excellent rubber tear but not asgood as the carcass-to-carcass samples. TABLE 9 180° Peel Test Data forRubber-to-Rubber Bonding Using Sanded Carcass and Tread Stocks. Amountof Load at Max. Energy to Sample Type Monomer (ml) Load (N) Break (J)Tread/Tread 0.12 146.41 29.31 Tread/Tread 0.12 146.12 29.34 Tread/Tread0.12 118.27 21.51 Mean 136.93 26.72 Carcass/Carcass 0.16 362.55 50.16Carcass/Carcass 0.16 421.78 53.61 Carcass/Carcass 0.16 296.06 45.30 Mean360.13 49.69 Carcass/Tread 0.14 287.73 58.74 Carcass/Tread 0.14 300.8756.43 Carcass/Tread 0.15 218.00 43.35 Mean 268.86 52.84

EXAMPLE 23 Metal-to-Metal Bonding

[0153] A catalyst solution was prepared by dissolving 0.021 g ofRuCl₂(PCy₃)₂═CHPh in 1.5 ml of CH₂Cl₂. The catalyst solution was appliedto three grit-blasted steel coupons that were then bonded to othergrit-blasted steel coupons with 0.02-0.03 ml of ENB monomer per couponas described in Example 1, except that the monomer was applied to thecatalyst coated metal coupon. The other steel coupon was immediatelymated to the treated surface and weighted down with a 100 g weight.After three days of sitting at ambient conditions, all three samplescould not be pulled apart by hand. The samples were analyzed on anInstron using a lap shear tensile test and showed a mean load at breakof 375.99 (N).

EXAMPLE 24 Glass-to-Glass Bonding

[0154] A catalyst solution was prepared by dissolving 0.040 g ofRuCl₂(PCy₃)₂═CHPh in 3.0 ml of CH₂Cl₂. The catalyst solution was appliedto three glass microscope slides that were then bonded to other glassmicroscope slides with 0.15-0.20 ml of ENB monomer per slide asdescribed in Example 1, except that not all the catalyst solution wasused—just a sufficient amount to cover the defined area. The solvent wasallowed to evaporate for 3 to 4 minutes before the ENB was pipetted ontothe catalyst containing surface. Immediately, the other glass slide wasmated onto the other slide and held in place with a 100 g weight. After1.5 hours, the two glass slides were examined and found to be heldtogether as the substrates could be picked up without falling apart.

EXAMPLE 25 Paper-to-Paper Bonding

[0155] A catalyst solution prepared from 0.040 g of RuCl₂(PCy₃)₂═CHPh in3 ml of CH₂Cl₂ was applied to a single piece of laboratory filter paperas described in Example 1. The solvent was allowed to evaporate forapproximately 2 minutes. ENB monomer was applied to another piece offilter paper. Immediately, the two paper surfaces were mated and held inplace with a 100 g weight. After 1.5 hours, the two paper pieces wereexamined and found to be held together and could not be pulled apart.

Example 26 Spray Application of RuCl₂(PCy₃)₂═CHPh and Coating Formationusing ENB on Various Substrates

[0156] A catalyst solution was prepared by dissolving 0.75 g ofRuCl₂(PCy₃)₂═CHPh in 25 ml of CH₂Cl₂. This solution was then sprayapplied onto a 7.62 cm×15.24 cm substrate surface, which had beenpreviously wiped with acetone to remove any surface contamination, in asweeping pattern until even-appearing coverage was obtained. The solventwas allowed to evaporate for 30 minutes in the open laboratoryatmosphere leaving the surface coated with catalyst. Black Santoprene®,manila Santoprene®, acrylonitrile butadiene styrene (ABS),polypropylene, polymethylmethacrylate (PMMA), aluminum, chromatedaluminum, stainless steel, polycarbonate sheet, Delrin acetal resinsheet, Mannington Classic uncoated embossed polyvinyl (PVC) flooring(designated “MC”), and Tarkett/Domco polyvinyl flooring (designated “T”)were sprayed with ENB monomer and allowed to dry. Both static andkinetic coefficients of friction of all the coated specimens weremeasured by determining drag resistance on an Instron (see P. R. Guevin,“Slip Resistance,” in Paint and Coating Testing Manual, FourteenthEdition of the Gardner-Sward Handbook, J. V. Koleske, ed., ASTM ManualSeries: MNL 17,ASTM, Philadelphia, 1995, Chapter 50.) The results areshown below in Tables 10 and 11. For all samples the static and kineticcoefficients of friction were lower after spray coating with ENBcompared to the control (e.g., shown in the Table as Aluminum-C) of thatsample except in a few cases. Lower static and kinetic coefficients offriction indicate improved surface lubricity. TABLE 10 Static andKinetic Coefficient of Friction Results for Metal Substrates SprayCoated with ENB. Static COF Static COF Kinetic COF Kinetic COF Sample IDMean Std Dev Mean Std Dev Aluminum-1 0.440 0.086 0.107 0.011 Aluminum-20.307 0.078 0.155 0.017 Aluminum-3 0.277 0.041 0.143 0.013 Aluminum-40.244 0.047 0.154 0.042 Aluminum-C 0.746 0.150 0.242 0.118 Chromated0.263 0.093 0.112 0.025 Aluminum-1 Chromated 0.287 0.039 0.162 0.018Aluminum-2 Chromated 0.341 0.076 0.095 0.018 Aluminum-3 Chromated 0.2560.042 0.152 0.014 Aluminum-4 Chromated 0.755 0.430 0.233 0.138Aluminum-C Stainless 0.397 0.062 0.119 0.013 Steel-1 Stainless 0.2970.049 0.119 0.005 Steel-2 Stainless 0.259 0.031 0.131 0.015 Steel-3Stainless 0.256 0.063 0.121 0.005 Steel-4 Stainless 0.244 0.008 0.1840.006 Steel-C

[0157] TABLE 11 Static and Kinetic Coefficient of Friction Results forPlastic Substrates Spray Coated with ENB. Static Static Kinetic COF COFCOF Kinetic COF Sample ID Mean Std Dev Mean Std Dev ABS-1 0.216 0.0680.073 0.011 ABS-2 0.436 0.224 0.075 0.048 ABS-3 0.343 0.108 0.077 0.032ABS-4 0.172 0.023 0.086 0.015 ABS-C 0.291 0.021 0.163 0.011 Delrin-10.550 0.067 0.215 0.039 Delrin-2 0.475 0.080 0.188 0.012 Delrin-C 0.5990.023 0.521 0.031 EPDM-1 0.535 0.088 0.265 0.040 EPDM-2 0.630 0.0780.305 0.034 EPDM-3 0.749 0.069 0.174 0.015 EPDM-4 0.296 0.031 0.1830.012 EPDM-C 2.547 0.036 1.997 0.896 MC-1 0.514 0.063 0.419 0.084 MC-20.631 0.187 0.334 0.022 MC-3 0.654 0.097 0.465 0.025 MC-4 0.589 0.0610.399 0.042 MC-C 1.810 0.198 1.031 0.243 Polycarbonate-1 1.364 0.1420.083 0.000 Polycarbonate-2 0.989 0.048 0.164 0.048 Polycarbonate-30.674 0.162 0.178 0.028 Polycarbonate-4 0.211 0.034 0.187 0.000Polycarbonate-C 0.963 0.263 0.301 0.011 PMMA-1 0.392 0.156 0.083 0.031PMMA-2 0.322 0.187 0.086 0.027 PMMA-3 0.433 0.108 0.150 0.054 PMMA-40.402 0.176 0.083 0.000 PMMA-C 0.517 0.062 0.386 0.018 Polypropylene-10.174 0.029 0.040 0.057 Polypropylene-2 0.145 0.016 0.110 0.026Polypropylene-3 0.187 0.044 0.122 0.010 Polypropylene-4 0.161 0.0410.077 0.019 Polypropylene-C 0.394 0.056 0.225 0.057 Black Santoprene-10.369 0.064 0.143 0.009 Black Santoprene-2 0.332 0.026 0.145 0.064 BlackSantoprene-3 0.290 0.022 0.100 0.027 Black Santoprene-4 0.253 0.0080.099 0.021 Black Santoprene-C 2.581 0.033 2.204 0.115 ManilaSantoprene-1 0.282 0.021 0.080 0.011 Manila Santoprene-2 0.364 0.0260.107 0.072 Manila Santoprene-3 0.272 0.023 0.112 0.021 ManilaSantoprene-4 0.287 0.037 0.080 0.010 Manila Santoprene-C 1.050 0.0631.065 0.562 T-1 1.379 0.162 0.579 0.022 T-2 1.317 0.129 0.530 0.058 T-C4.328 0.300 −0.016 0.023

[0158] Adhesion measurements were determined by scoring a crosshatchpattern with a razor blade lightly into the coating surface. Five linesapproximately 3.2 mm apart and another five lines approximately 3.2 mmapart in crossing pattern. A 50.8-63.5 mm long strip of 25.4 mm widthScotch masking tape (2500-3705) was applied over the crosshatched areaand pressed smooth with a finger. After a second or two the tape waspulled quickly from the surface. An adhesion ranking scale was set upwith 1 being the best and 5 being the worst (see Table 12). TABLE 12Crosshatch Adhesion Test Definitions. Value Description 1 Veryexcellent-nothing on tape 2 Excellent-just crosshatch pattern 3Good-crosshatch pattern and specks at edges 4 Fair-crosshatch andbetween lines 5 Poor-everything pulled up

[0159] Adhesion ratings of poly(ENB) coating to rubbery substrates suchas Santoprene® and EPDM are shown in Table 13. They show that bothSantoprene® specimens gave excellent adhesion with only crosshatchpattern seen on the tape. EPDM adhesion was only a 4 with a single poorcoating and 1 with a second uniform coating. As long as a good uniformcoating of poly(ENB) was applied, good adhesion to rubbery substrateswas observed. TABLE 13 Crosshatch Adhesion Test Results for Poly(ENB)Coatings on Various Substrates. Sample ID Adhesion rating Type ofSubstrate Manila Santoprene-4 2 rubbery Black Santoprene-1 2 rubberyEPDM-1 4 rubbery EPDM-4 1 rubbery Aluminum-4 2 metal ChromatedAluminum-4 2 metal Stainless Steel-4 1 metal Polypropylene-4 2 plasticABS-4 1 plastic Propylene Carbonate-4 1 plastic PMMA-1 2 plastic MC-4 5flooring T-2 5 flooring Delrin-2 5 flooring Silicon Wafer 2 inorganicTeflon 1-2 plastic

EXAMPLE 27 Spray Application of RuCl₂(PCy₃)₂═CHPh and Formation ofLayered Coatings

[0160] A catalyst solution was prepared by dissolving 0.75 g ofRuCl₂(PCy₃)₂═CHPh in 25 ml of CH₂Cl₂. This solution was then sprayapplied onto the surface of four 7.62 cm×15.24 cm pieces of EPDM, whichhad been previously wiped with acetone to remove any surfacecontamination, in a sweeping pattern until even-appearing coverage wasobtained. The solvent was allowed to evaporate for 30 minutes in theopen laboratory atmosphere leaving the surface coated with catalyst. Thesamples were then sprayed with ENB monomer and allowed to stand in theopen laboratory atmosphere until not tacky. More ENB was applied toEPDM-4 and the sample allowed to dry overnight. The catalyst andresultant polymer levels are reported in Table 14. The increase incoating weight after the second spraying of ENB on EPDM-4 demonstratedthat layers of poly(ENB) could be built up on previous a EPDM surfaceand that the catalyst remained active. TABLE 14 Catalyst and MonomerLevels for Catalyst/ENB Coated EPDM Samples. Sub- strate Catalyst SampleID wt (g) wt (g) 1^(st) Polymer wt (g) 2^(nd) Polymer wt (g) EPDM-143.1487 0.0258 0.0555 EPDM-2 43.4636 0.0260 0.0393 EPDM-3 42.6556 0.02360.0365 EPDM-4 43.9878 0.0264 0.0440 0.2332

EXAMPLE 28 Spray Application of RuCl₂(PCy₃)₂═CHPh and Formation ofCoatings with Other Monomers

[0161] A catalyst solution was prepared by dissolving 0.75 g ofRuCl₂(PCy₃)₂═CHPh in 25 ml of CH₂Cl₂. This solution was then sprayapplied onto the surface of an ABS specimen (10.16 cm×15.24 cm), whichhad been previously wiped with isopropanol to remove any surfacecontamination, in a sweeping pattern until even-appearing coverage wasobtained. The solvent was allowed to evaporate for 30 minutes in a fumehood in the open laboratory atmosphere leaving the surface coated withcatalyst. The samples were then sprayed with DCPD, withmethylidenenorbornene (MNB), and cyclooctene (CO) monomers and allowedto stand in the open laboratory atmosphere for 2.5 hours beforeweighing. The catalyst and resultant polymer levels are reported inTable 15. Coefficient of friction data and cross-hatch adhesion data arereported in Tables 15 and 16, respectively. For the cyclooctenespecimen, no polymer formation was observed; the cyclooctene appeared tovolatilize from the surface. TABLE 15 Coefficient of Friction Data forDifferent Monomers Spray Applied to ABS. Static Static Kinetic KineticCatalyst Polymer wt COF COF COF COF Monomer wt (g) (g) Mean std dev Meanstd dev DCPD 0.167 0.948 0.25 0.03 0.11 0.01 MNB 0.125 0.142 0.27 0.080.10 0.01 CO 0.248 — 0.27 0.08 0.10 0.01

[0162] TABLE 16 Cross-Hatch Adhesion Dataa for Different Monomers SprayApplied to ABS. Monomer Adhesion Rating DCPD 1 MNB 3

EXAMPLE 29 Coating Formation using MoTB Catalyst and ENB

[0163] A catalyst solution was prepared by dissolving 0.1692 g of2,6-diisopropyl-phenylimido neophylidene molybdenum (VI) bis-t-butoxide(MoTB) in 5 ml of CH₂Cl₂. The catalyst solution was applied to a 10.16cm×15.24 cm ABS substrate in the glove box as described in Example 12.The catalyst thickened and the surface roughened with thick brush marksbecause the solvent dissolved the ABS surface. Using a pipette, ENBmonomer was applied in front of a 1 mil draw down bar and the bar waspulled down across the catalyst coated area. Upon attempting to drawdown the bar a second time, the newly formed coating scratched becausethe monomer polymerized so quickly. This gave a wrinkled, dark browncoating in the catalyst coated area and a chalky yellow edge were theENB monomer did not touch.

[0164] To eliminate this surface dissolution problem, another MoTBcatalyst solution (0.1192 g of MoTB in 3 ml CH₂Cl₂) was again applied toa surface, but this time to a 10.16 cm×15.24 cm chromated aluminum (AC)substrate. A more uniform coating of poly(ENB) formed on the surface.The chromated alumina coated specimen (AC) showed a static coefficientof friction of 0.44±0.03 and a kinetic coefficient of friction of 0.14±0.05. These data were obtained for the AC specimen only as the ABSsurface was too rough as described above. Cross-hatch adhesion data forboth specimens are reported in Table 17. TABLE 17 Cross-Hatch AdhesionDataa for Different Monomers/Substrates. Monomer Substrate AdhesionRating ENB ABS 4 ENB AC 3

EXAMPLE 30 Coatings by Application of Catalyst or Monomer in a PolymerMatrix

[0165] A matrix solution was prepared (2 g of PMMA, 0.1 g ofRuCl₂(PCy₃)₂═CHPh, and 50 ml of CH₂Cl₂) and applied by spray applicationto a PMMA substrate. The coating was not uniform so three to four dropsof the above matrix solution were applied to the PMMA substrate andspread out using a glass rod. On drying, a clear uniform coating formedwhich was sprayed with ENB.

[0166] Changes in surface tension of the coatings were evaluated using aset of Accu-Dyne solutions. These solutions are used to match theirsurface tensions with the surface in question. A match in surfacetension is determined when the applied solution wets the surface beingtested. The surface tension of the solution then correlates with thesurface tension of the surface.

[0167] No change in surface tension was observed before and afterspraying ENB on the PMMA/RuCl₂(PCy₃)₂═CHPh matrix described above (γ=38dynes/cm). More RuCl₂(PCy₃)₂═CHPh was added to thePMMA/RuCl₂(PCy₃)₂═CHPh matrix thus bringing the total to 0.35 g catalystin the PMMA matrix. This new solution was coated onto new 5.08 cm×5.08cm PMMA substrate, dried, and then sprayed with ENB. The surface tensionremained 38 dynes/cm. Again, another addition of catalyst brought thenew total to 0.55 g RuCl₂(PCy₃)₂═CHPh in the PMMA matrix. This surface,which was processed as described above, displayed a surface tension of34 dynes/cm. This result demonstrated that the catalyst remained activewhen incorporated into a polymer matrix and that coatings can be appliedover this active surface.

[0168] A solution containing 0.25 g of RuCl₂(PCy₃)₂═CHPh in 15 ml ofCH₂Cl₂ was sprayed onto a 10.16 cm×15.24 cm PMMA substrate surface toprovide 0.0384 g of catalyst onto the surface on drying. The overcoatPMMA/ENB matrix (2 ml of ENB, 1 gm of PMMA, in 10 ml of CH₂Cl₂) wasapplied by glass rod to the catalyst coated surface and the resultingsurface tension was 46 dynes/cm). This compares to a surface tension of36 dynes/cm for a control uncoated PMMA substrate.

EXAMPLE 31 Coating Paper by Spray Application of RuCl₂(PCy₃)₂═CHPh andDifferent Monomers

[0169] Commercial filter paper (Whatman #41) samples were cut intofifteen dogbone-shaped specimens (11 cm overall length, 40×7.2 mm drawarea) and spray coated with a solution of RuCl₂(PCy₃)₂═CHPh as describedin Example 8. After drying in the laboratory air for 30 minutes, thespecimens were weighed, and then five specimens were spray coated withDCPD (5 ml), five specimens were spray coated with ethylidenenorbornene(8 ml), and five specimens were spray coated with cyclooctene (5 ml) onone side of the paper. After drying for 16 hours in the fume hood, thespecimens were weighed to determine the amount of reacted monomer andtheir tensile properties determined on an Instron (Table 18). Poly(ENB)and poly(DCPD) coated paper dog-bones showed increased maximum loadvalues, while poly(cyclooctene) did not. Statistical analysis (t-test)revealed increased displacement at maximum load for DCPD at the 95%confidence level. Little poly(cyclooctene) formed likely as a result ofits high volatility vs ROMP rate. TABLE 18 Tensile Strength Data forPaper Dog-Bone Specimens^(a). Displacement at Load at max catalystcoating max load (mm) load (Kgf) ID Monomer amt (g) amt (g) [mean/sd][mean/sd] A ENB 0.0072 0.0941 0.624 0.187 2.636 0.190 B DCPD 0.00660.0949 0.644 0.083 3.401 0.661 C cyclooctene 0.0060 0.0018 0.574 0.0470.894 1.064 D — — — 0.514 0.051 1.024 0.189

EXAMPLE 32 Fiber Coating by Application of RuCl₂(PCy₃)₂=CHPh and Monomer

[0170] Kevlar®, Nomex®, and nylon threads (size 69, 0.2032 mm) were cutinto 30.48 cm lengths, soaked in a solution containing approximately0.04 g of RuCl₂(PCy₃)₂═CHPh in 5 ml of CH₂Cl₂ for one minute, andallowed to dry in a straight position. After 20 minutes the threads weresprayed with 8 ml of ENB. After two hours the threads appeared straightand stiff. Tensile properties for these specimens were compared touncoated threads on an Instron (Table 19). No real differences intensile data were observed. However, each thread was thicker providingevidence that the threads were indeed coated. TABLE 19 TensileProperties of ENB Coated and Uncoated Threads. Load @ Max ThicknessThread Load (Kg) Max. % Strain (mm)^(a) Kevlar 3.947 ± 1.089  9.310 ±2.354 0.27 Kevlar-coated 4.330 ± 0.008 10.659 ± 1.056 0.31 Nylon 2.633 ±0.477  59.069 ± 17.614 0.26 Nylon-coated 2.601 ± 0.651 31.154 ± 8.3240.30 Nomex 1.893 ± 0.129 31.289 ± 3.006 0.27 Nomex-coated 2.018 ± 0.26030.452 ± 6.182 0.28

EXAMPLE 33 Fabric Coating by Application of RuCl₂(PCy₃)₂═CHPh andMonomer

[0171] Strips of cotton, fiberglass, polyester, and aramid fabric werecut to 2.54 cm×15.24 cm geometries, dipped in a solution containing 1.0g of RuCl₂(PCy₃)₂═CHPh in 100 ml of CH₂Cl₂ for one minute, and allowedto dry. It was noted that excess catalyst wicked to the fabric surfacesduring the drying process. The excess catalyst was shaken from eachfabric. All fabrics had a purple color showing that catalyst hadadsorbed onto the surface. Approximately 30 ml of ENB was sprayed ontoboth sides of the fabric strips. All fabric samples stiffened as thepolymerization occurred. Tensile properties were determined for six ofeach coated and uncoated specimen on an Instron (Table 20). While stiff,the fabrics could easily be bent like uncoated fabric.

[0172] By coating poly(ENB) on the polyester fabric the load at peakalmost doubled, but differences in displacement or % strain were slight.This suggests that the strength of the tightly woven polyester fabric isincreased strictly by addition of poly(ENB). Aramid and cotton fabricsshowed displacement and % strain at peak to be halved and load at peakto be slightly increased or no change, respectively. Thus, these fabricslose some of their stretchability by the addition of poly(ENB), but losenone of their strength. For fiberglass, the load at peak and energy tobreak increase significantly, while displacement and % strain at peakshow no change. TABLE 20 Tensile Properties of ENB Coated and UncoatedFabrics^(a). Displacement % Strain at Energy to Material at Peak (mm)Peak (%) Load at Peak Break (J) ID Type [mean/sd] [mean/sd] (kN)[mean/sd] [mean/sd] Control Polyester 10.882 0.481 42.841 1.892 0.8890.045 7.036 0.577 8165-27 A Polyester 11.575 0.181 45.571 0.712 1.5110.076 7.723 0.866 Control Aramid 15.500 0.746 61.417 2.937 0.168 0.0081.397 0.072 8165-27 B Aramid 8.282 1.616 32.605 6.364 0.237 0.019 1.7580.289 Control Cotton 6.972 0.404 27.448 1.590 0.702 0.022 2.102 0.2188165-27 C Cotton 3.380 0.470 13.307 1.850 0.805 0.106 1.951 0.227Control Fiberglass 2.925 0.034 11.516 1.197 0.641 0.085 1.841 0.8588165-27 D Fiberglass 3.050 0.166 12.008 0.653 1.917 0.203 8.669 3.042

EXAMPLE 34

[0173] Synthesis of Bisnorbornadiene Crosslinker # 49

[0174] A 250 ml, 14/20, 3-neck, round-bottom flask was fitted with athermometer, rubber septum and reflux condenser with gas adapter. Astirring bar was added. The system was flame-dried under argon and leftunder argon. To this apparatus was charged 5.000 grams (0.0115 moles) of4-ethyl-2,3,5,6-tetrabromotoluene and 130 ml of distilled diethyl ether.The tetrabromotoluene dissolved to form a clear, light-yellow solution.

[0175] The reaction flask contents were cooled to −62° C. in a2-propanol/dry-ice bath and was charged with 9.5 ml (7.620 grams, 0.1153moles, 10.0 equiv.) of cyclopentadiene. Finally, 9.5 ml (0.0237 moles,2.1 equiv.) of 2.5M n-BuLi solution in hexanes was added to the reactionflask dropwise over a 40 minute period using a gas-tight syringe. Thereaction mixture was slowly brought to room temperature and stirredovernight, then quenched with 1.5 ml of MeOH, vacuum filtered, andwashed with deionized, distilled water (3×25 ml). The cloudy-yelloworganic layer was dried with MgSO₄ and vacuum filtered. The filtrate wasrotoevaporated at 39° C. under partial vacuum to give a clear, goldliquid, which under high vacuum gave a yellow solid. . The solid waswashed with cold MeOH (3×15 ml) to give a cream colored powder. Dryingunder vacuum gave 1.617 grams (57% yield) of product. ¹H and ¹³C—NMRconfirmed that the product had been synthesized in high purity. TheNMR's also showed that the product was a mixture of both syn andanti-isomers. M. P. =84-85° C.; ¹H NMR (CDCl₃): δ 1.18 (3H), 2.28 (7H),2.75 (2H), 3.99 (4H), 6.85 (4H); ¹³C NMR (CDCl₃): δ 14.8, 16.5, 23.1,47.9, 48.0, 48.2, 69.8, 123.0, 123.1, 129.6, 129.7, 143.2, 143.4, 145.8,146.6.

[0176] Synthesis of Structure # 48

[0177] The same procedure was used as for Crosslinker # 49, except that5.000 grams (0.0111 moles) of 1,4-diethyl-2,3,5,6-tetrabromobenzene and130 ml of distilled diethyl ether were initially charged into thereaction flask; 9.1 ml (7.299 grams, 0.1104 moles, 9.9 equiv.) ofcyclopentadiene, and 9.5 ml (0.0237 moles, 2.1 equiv.) of 2.5M n-BuLisolution in hexanes were charged into the reaction flask dropwise over a40 minute period dissolved in ENB, and applied to each strip asdescribed in Example 4. The EPDM rubber strips were washed with acetoneand allowed to dry prior to application of the metathesizable mixtureThree strips (34.9 mm×25.4 mm) were bonded and tested on an Instronusing the 180° Peel Test at the peel temperature noted in TABLE 21.TABLE 21 Substrates Peel test Max. Load Crosslinker EX. Crosslink BondedTemp. (° C.) (lbf) Conc. Comment 34 A Control Tire Carcass / −40 118.895− stretched (none) Tread 34 B #48 Tire Carcass / −40 117.595  2.8 mole %stretched Tread (satd.) 34 C #49 Tire Carcass / −40 146.607  3.4 mole %broke Tread 34 D Control Tire Carcass / 23 70.070 − deep tear (none)Tread or broke 34 E #47 Tire Carcass / 23 59.437  7.9 mole % deep tearTread (satd.) or broke 34 F #48 Tire Carcass / 23 84.907  2.8 mole %broke or Tread (satd.) stretched 34 G #48 Tire Carcass / 23 83.526  0.5mole % broke Tread 34 H #49 Tire Carcass / 23 78.235  3.4 mole % brokeTread 34 I #49 Tire Carcass / 23 61.266 19.6 mole % deep tear Tread orbroke 34 J Control Tire Carcass / 66 10.160 — no rubber (none) Treadtear 34 I #47 Tire Carcass / 66 52.749  7.9 mole % deep tear Tread(satd.) or broke 34 J #48 Tire Carcass / 66 52.308  2.8 mole % brokeTread (satd.) 34 K #49 Tire Carcass / 66 17.627  0.5 mole % no rubberTread tear 34 L #49 Tire Carcass / 66 45.048  3.4 mole % deep tear Treador broke 34 M #49 Tire Carcass / 66 21.899 19.6 mole % no rubber Treadtear 35 A Control EPDM / EPDM 23 39.602 − deep tear (none) 35 B #48 EPDM/ EPDM 23 44.453  0.5 mole % rubber tear 35 C Control EPDM / EPDM 6622.312 − rubber (none) tear 35 D #48 EPDM / EPDM 66 23.707  0.5 mole %rubber tear 35 E #48 EPDM / EPDM 66 22.047  2.8 mole % rubber (satd.)tear 34 N #47 Tire Carcass / 85 25.338  7.9 mole % rubber Tread (satd.)tear 34 O #48 Tire Carcass / 85 20.906  3.4 mole % rubber Tread (satd.)tear 34 P #49 Tire Carcass / 85 15.284 19.6 mole % no rubber Tread tear36 A Control EPDM / Metal −40 74.156 — no tear or (none) stock break* 36B #48 ″ −40 87.825  0.5 mole % no tear or stock break* 36 C Control ″ 2363.816 — good rubber tear 36 D #48 ″ 23 72.348  0.5 mole % good tear orstock break 36 E Luperox ® ″ 23 84.378  1.2 mole % stretched 130 orstock break 36 F Control ″ 66 18.963 — little (none) rubber tear 36 G#48 ″ 66 29.983  0.5 mole % good rubber tear 36 H Luperox ″ 66 37.155 1.2 mole % rubber 130 tear

[0178] With reference to FIG. 5, illustrating improvement in hightemperature adhesion, the peel strength at below and room temperature isnot sacrificed, while peel strength at elevated temperatures is improvedby incorporation of crosslinker into the metathesizable material whichundergoes contact metathesis polymerization.

EXAMPLE 37

[0179] Adhesives containing a monomer or solution mixture with variouscrosslinking monomers were used to bond sanded and unsandedpolypropylene via CMP. Lap shear samples were prepared from4″1″×{fraction (1/8)}″ coupons according to the following procedure. Ifthe polypropylene was sanded, 100 grit sandpaper was used to lightlyroughen the bonding area of the lap shear samples. A solution of 200 mgof bis(tricyclohexylphosphinebenzylidene ruthenium(II) dichloride(Grubbs' catalyst) ortricyclohexylphosphine(1,3-demesityl-4,5-dihydroimidazol-2-ylidene)benzylideneruthenium(II) dichloride in 15 mL of dichloromethane was sprayed ontothe 1 in² bonding area of 10 polypropylene coupons. After the solventwas dry, about 3.5 to 4.0 mg of catalyst had been delivered to eachcoupon. About 150 μL of monomer(s) was placed on the conjugate coupon,the catalyst-containing coupon and the monomer-containing coupons weremated, and the adhesive was allowed to cure for 24 hours. A set of fivelap shear samples was prepared for each monomer. The results are shownin the table 22 below. TABLE 22 Lap shear results on polypropylene (PP).Where indicated, ratios are on a mass basis for the monomer mixture.Unsanded PP Sanded PP Crosslinking Mean Stress at Break in Mean Stressat Break in Monomer p.s.i. p.s.i. Catalyst (Standard Deviation)(Standard Deviation) (mass ratio) Failure Mode Failure Mode Crosslinkers

68 (9) Not Studied

73 (4) Adhesive Not Studied

Not Studied 407 (32) Adhesive Secondary Crosslinkers

Not Studied 308 (41) Adhesive

Not Studied 443 (14) Adhesive/Stock Break

224 (82) Adhesive 399 (99) Cohesive

245 (103) Adhesive 493 (76) Stock Break

264 (23) Adhesive Not Studied

429 (99) Adhesive Not Studied

EXAMPLE 38

[0180] Additional adhesive tests on PP were performed. The control wasENB alone. Examples according to the invention included a mixture of ENBand crosslinking metathesizable comonomer. Lap shear results with ENBand norbomadiene-based dimer on sanded polypropylene are given in Table23. Improvements are seen with the mixtures containing metathesizablecrosslining comonomer, evidencing the contribution of crosslinks to bondstrengths when adhereing PP to itself. Monomer Stress at max. loadStandard deviation Controol ENB 348 psi 38 psi 98% ENB/2% dimer 406 psi48 psi 95% ENB/5% dimer 405 psi 23 psi 90% ENB/10% dimer 407 psi 32 psi

What is claimed is:
 1. A method for bonding a first substrate to asecond substrate comprising: (a) providing a metathesis catalyst at thefirst substrate to form a treated first substrate; (b) providing ametathesizable mixture containing 0.5-20 mol % of a metathesizablecrosslinker dissolved in a principal metathesizable material, on saidsecond substrate or as a component of the second substrate; and (c)joining said treated first substrate with said second substrate with themetathesizable material there between whereby the metathesizablematerial initiates a metathesis reaction to form a crosslinked polymerbonding the first substrate to the second substrate.
 2. A methodaccording to claim 1 wherein at least one of the substrates comprises anelastomeric material.
 3. A method according to claim 2 wherein theelastomeric material is a thermoplastic elastomer.
 4. A method accordingto claim 1 wherein one of the first or second substrates comprises ametallic material and the other first or second substrate comprises anelastomeric material.
 5. A method according to claim 4 wherein themetallic material comprises steel and the elastomeric material isselected from natural rubber, polychloroprene, polybutadiene,polyisoprene, styrene-butadiene copolymer rubber,acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymerrubber, ethylene-propylene-diene terpolymer rubber, butyl rubber,brominated butyl rubber, alkylated chlorosulfonated polyethylene rubber,hydrogenated nitrile rubber, silicone rubber, fluorosilicone rubber,poly(n-butyl acrylate), thermoplastic elastomer and mixtures thereof. 6.A method according to claim 1 wherein the first substrate comprises atire carcass and the second substrate comprises a tire tread.
 7. Amethod according to claim 1 wherein step (b) comprises applying themetathesizable mixture to the second substrate surface and step (c)comprises contacting the catalyst on the first substrate surface and thetreated second substrate surface.
 8. A method according to claim 1wherein at least one of the substrates is substantially curedelastomeric material.
 9. A method according to claim 1 wherein themetathesizable mixture comprises (a) and (b) wherein (a) is selectedfrom the group consisting of norbornene, methylidenenorbornene,ethylidenenorbornene, norbornadiene, dicyclopentadiene, cyclooctene,cyclohexenyl norbornene and (b) is selected from the group consisting of


10. A method according to claim 1 wherein step (c) is conducted atambient temperature.
 11. A method according to claim 1 wherein steps(a)-(c) occur at room temperature.
 12. A method according to claim 6wherein the bonding in step (c) occurs within one hour.
 13. A methodaccording to claim 1 wherein step (a) comprises applying a catalyst ontothe first substrate surface.
 14. A method according to claim 13 whereinthe metathesis catalyst is dissolved or mixed into a liquid carrierfluid and applied to the first substrate and the liquid or carrier isremoved prior to step (c).
 15. A method according to claim 13 whereinthe metathesis catalyst is included as a component in a multi-componentcomposition.
 16. A method according to claim 1 wherein the metathesiscatalyst is included as a component of the first substrate.
 17. A methodaccording to claim 7 wherein the principal metathesizable material is inthe form of a liquid, paste or meltable solid.
 18. A method according toclaim 7 wherein the principal metathesizable material is included as acomponent in a multi-component composition.
 19. A method according toclaim 1 wherein the principal metathesizable material is included as acomponent of the second substrate.
 20. A method for bonding a metallicsubstrate to an elastomeric substrate comprising: (a) applying a solidmetathesis catalyst to a portion of the metallic substrate surfaceforming a treated metallic substrate; (b) applying a metathesizablemixture comprising a metathesizable crosslinking monomer dissolved in aprincipal metathesizable material to the elastomeric substrate surface;and (c) bringing the metallic substrate surface and the elastomericsubstrate surface together to contact the catalyst and themetathesizable material, thereby initiating a metathesis polymerizationand crosslinking reaction.
 21. A method according to claim 20 whereinstep (c) occurs at ambient temperature.
 22. A method according to claim20 wherein the elastomeric substrate is a substantially curedelastomeric material.
 23. A method according to claim 1 wherein themetathesis catalyst is selected from at least one of a rhenium compound,ruthenium compound, osmium compound, molybdenum compound, tungstencompound, titanium compound, niobium compound, iridium compound andMgCl₂.
 24. A method according to claim 23 wherein the metathesiscatalyst is selected from a ruthenium compound, a molybdenum compound,iridium compound and an osmium compound.
 25. A method according to claim24 wherein the metathesis catalyst has a structure represented by

wherein M is Os, Ru or Ir; each R¹ is the same or different and is H,alkenyl, alkynyl, alkyl, aryl, alkaryl, aralkyl, carboxylate, alkoxy,alkenylalkoxy, alkenylaryl, alkynylalkoxy, aryloxy, alkoxycarbonyl,alkylthio, alkylsulfonyl or alkylsulfinyl; X is the same or differentand is an anionic ligand group; and L is the same or different and is aneutral electron donor group.
 26. A method according to claim 25 whereinX is Cl, Br, I, F, CN, SCN, or N₃; L is Q(R²)_(a) wherein Q is P, As, Sbor N; R² is H, cycloalkyl, alkyl, aryl, alkoxy, arylate or aheterocyclic ring; and a is 1, 2 or 3; M is Ru; and R¹ is H, phenyl,—CH═C(phenyl)₂, —CH═C(CH₃)₂ or —C(CH₃)₂(phenyl).
 27. A method accordingto claim 26 wherein the metathesis catalyst is a phosphine-substitutedruthenium carbene.
 28. A method according to claim 27 wherein thecatalyst is bis(tricyclohexylphosphine)benzylidene ruthenium (IV)dichloride.
 29. A method according to claim 1 wherein the metathesiscatalyst is stable in the presence of moisture and oxygen and caninitiate polymerization of the metathesizable material upon contact atroom temperature.
 30. A method according to claim 1 wherein theprincipal metathesizable material includes at least one reactiveunsaturated metathesizable functional group.
 31. A method according toclaim 30 wherein the principal metathesizable material comprises anolefin.
 32. A method according to claim 31 wherein the principalmetathesizable material is selected from ethene, α-alkene, acyclicalkene, acyclic diene, acetylene, cyclic alkene, cyclic polyene andmixtures thereof.
 33. A method according to claim 32 wherein theprincipal metathesizable material comprises a cycloolefin.
 34. A methodaccording to claim 33 wherein the principal metathesizable material is amonomer or oligomer selected from norbornene, cycloalkene,cycloalkadiene, cycloalkatriene, cycloalkatetraene, aromatic-containingcycloolefin and mixtures thereof.
 35. A method according to claim 34wherein the metathesizable material is a norbornene monomer or oligomer.36. A method according to claim 35 wherein the norbornene has astructure represented by

wherein X is CH₂, CHR³, C(R³)₂, O, S, N—R³, P—R³, O═P—R³, Si(R³)₂, B—R³or As—R³; each R¹ is independently H, CH₂, alkyl, alkenyl, cycloalkyl,cycloalkenyl, aryl, alkaryl, aralkyl, halogen, halogenated alkyl,halogenated alkenyl, alkoxy, oxyalkyl, carboxyl, carbonyl, amido,(meth)acrylate-containing group, anhydride-containing group, thioalkoxy,sulfoxide, nitro, hydroxy, keto, carbamato, sulfonyl, sulfinyl,carboxylate, silanyl, cyano or imido; R²is a fused aromatic, aliphaticor heterocyclic or polycyclic ring; and R³ is alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy.
 37. A methodaccording to claim 36 wherein the principal metathesizable materialcomprises ethylidenenorbornene monomer or oligomer.
 38. A methodaccording to claim 1 wherein the principal metathesizable materialcomprises liquid ethylidenenorbornene monomer.
 39. A method according toclaim 1 wherein the catalyst is applied in an aqueous solution ormixture and the metathesizable material is applied in the form of aliquid that is substantially 100 percent reactive.
 40. A methodaccording to claim 1 wherein the method is substantially free of the useof volatile organic solvents.
 41. A method according to claim 20 whereinthe principal metathesizable material comprises norbornene monomer oroligomer having a structure represented by

wherein X is CH₂, CHR³, C(R³)₂, O, S, N—R³, P—R³, O═P—R³, Si(R³)₂, B—R³or As—R³; each R¹ is independently H, CH₂, alkyl, alkenyl, cycloalkyl,cycloalkenyl, aryl, alkaryl, aralkyl, halogen, halogenated alkyl,halogenated alkenyl, alkoxy, oxyalkyl, carboxyl, carbonyl, amido,(meth)acrylate-containing group, anhydride-containing group, thioalkoxy,sulfoxide, nitro, hydroxy, keto, carbamato, sulfonyl, sulfinyl,carboxylate, silanyl, cyano or imido; R²is a fused aromatic, aliphaticor heterocyclic or polycyclic ring; and R³ is alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl or alkoxy; and thecatalyst is selected from a ruthenium compound, a molybdenum compoundand an osmium compound.
 42. A method according to claim 41 wherein step(c) occurs at room temperature.
 43. A method according to claim 1wherein step (a) comprises applying a ruthenium catalyst in a liquidcarrier to the first substrate surface, step (b) comprises applying ametathesizable liquid norbornene monomer to the second substrate surfaceand step (c) comprises contacting the catalyst-applied first substratesurface and the monomer-applied second substrate surface.